Geochemical Modeling to Evaluate Remediation …...outgassing rate in -1sec Aer3: k a = 0.00056 s-1...

Geochemical Modeling to Evaluate Remediation Options for Iron-Laden Mine Discharges

Charles ldquoChuckrdquo Cravotta III US Geological Survey

Pennsylvania Water Science Center cravottausgsgov

 

 

 

Summary Aqueous geochemical tools using PHREEQC have been developed by USGS for OSMRErsquos ldquoAMDTreatrdquo cost-analysis software

uuml Iron-oxidation kinetics model considers pH-dependent abiotic and biological rate laws plus effects of aeration rate on the pH and concentrations of CO2 and O2

uuml Limestone kinetics model considers solution chemistry plus the effects of surface area of limestone fragments

uuml Potential water quality from various treatments can be considered for feasibility and benefitscosts analysis

Al3+

Fe2+ Fe3+

Mn2+ Active Passive

TREATMENT OF COAL MINE DRAINAGE

Increase pHoxidation with natural substrates amp microbial activity

Reactions slow

Large area footprint

Low maintenance

Increase pHoxidation with aeration ampor industrial chemicals

Reactions fast efficient

Moderate area footprint

High maintenance

ACTIVE TREATMENT 28 ndash aeration no chemicals (Ponds) 21 ndash caustic soda (NaOH) used 40 ndash lime (CaO Ca(OH)2) used 6 ndash flocculent or oxidant used 4 ndash limestone (CaCO3) used

PASSIVE TREATMENT

PASSIVE TREATMENT

Vertical Flow Limestone Beds Bell Colliery

Limestone Dissolution O2 Ingassing

CO2 Outgassing Fe(II) Oxidation amp Fe(III)

Accumulation

Pine Forest ALD amp Wetlands Silver Creek Wetlands

A Anthracite Mine Discharges

B Bituminous Mine Discharges

BIMODAL pH FREQUENCY DISTRIBUTION Fr

eque

ncy i

n pe

rcen

t N=9

9 Fr

eque

ncy i

n pe

rcen

t N=4

1 40

35

30

25

20

15

10

5

0

40

35

30

25

20

15

10

5

0

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH field

pH lab (aged)

pH increases after ldquooxidationrdquo of net alkaline water (CO2

outgassing) HCO3

- = CO2 (gas) + OH-

Anthracite AMD

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH

pH field

pH lab (aged) pH decreases after ldquooxidationrdquo

of net acidic water (Fe oxidation and hydrolysis)

Fe2+ + 025 O2 + 25 H2O rarr Fe(OH)3 + 2 H+

Bituminous AMD

AMDTreat

ldquoPHREEQ-N-AMDTREATrdquo httpamdosmregov

AMDTreat is a computer application for estimating abatement costs for AMD (acidic or alkaline mine

drainage)

AMDTreat is maintained by OSMRE

The current version of AMDTreat 50+ is being recoded from FoxPro to

C++ to facilitate its use on computer systems running

Windows 10 The PHREEQC geochemical models described below

will be incorporated to run with the recoded program

 

 

 

 

AMDTREAT 50+ bull With the ldquoPHREEQC chemical titration toolrdquo

AMDTreat 50+ has capability to estimate

uuml Quantity and cost of caustic chemicals to attain a target pH (without and with pre-aeration)

uuml Chemistry of treated effluent after reactions and

uuml Volume of sludge produced as the sum of precipitated metal hydroxides plus unreacted chemicals

 

 

 

AMDTREAT 50+ bull PHREEQ-N-AMDTreat ldquochemical titration

toolrdquo accurately relates caustic addition pH and metals solubility hellip but

uuml assumes instantaneous complete reactions without consideration of kinetics of gas exchange rates and

uuml ignores effects of changing pH on iron oxidation rate

AMDTreat 50+

Caustic Additionmdash

St Michaels

Discharge

Escape PresentaBon

 

 

ldquoNewrdquo PHREEQC Kinetics Models for AMDTreat 50+

uuml FeII oxidation model that utilizes established rate equations for gas exchange and pH-dependent iron oxidation and that can be associated with commonly used aeration devicessteps (including decarbonation)

uuml Limestone dissolution model that utilizes established rate equation for calcite dissolution and that can be adjusted for surface area of commonly used aggregate particle sizes

KINETICS OF IRON OXIDATION ndash pH amp GAS EXCHANGE EFFECTS

Iron Oxidation Kinetics are pH Dependent (abiotic and microbial processes can be involved)

(1996)

(Kirby et al 1999)

Cbact is concentraBon of iron-oxidizing bacteria in mgL expressed as dry weight of bacteria (28E-13 gcell or 28E-10 mgcell )

The AMDTreat FeII oxidaBon kineBc model uses most probable number of iron-oxidizing bacteria per liter (MPNbact)

Cbact = 150 mgL is equivalent to MPNbact = 53E11 where Cbact = MPNbact middot(28E-10)

Abiotic Homogeneous Fe(II) Oxidation Rate (model emphasizes pH)

Fe2+Fe(OH)2 0

Fe(OH)1+

Minutes Hours

Days

Months

Years

Between pH 5 and 8 the Fe(II) oxidation rate increases by

100x for each pH unit increase

At a given pH the rate increases by 10x for a 15 degC increase Using the activation energy of 23 kcalmol with the Arrhenius equation the rate

can be adjusted for temperature

Extrapolation of homogeneous rate law -d[Fe(II)]dt = k1 middot[Fe(II)]middot[O2]middot[H+]-2

k1 = 3 x 10-12 molLmin

log kT1 = log kT2 + Ea (2303 R) middot (1T2 - 1T1)

At [O2] = 026 mM (pO2 = 021 atm) and 25degC Open circles (o) from Singer amp Stumm (1970) and solid circles (bull) from Millero et al (1987)

Dashed lines are estimated rates for the various dissolved Fe(II) species

Effects of O2 Ingassing and CO2 Outgassing

on pH and Fe(II) Oxidation Rates

Batch Aeration Tests at Oak Hill Boreholes

(summer 2013)

Control Not Aerated Aerated H2O2 Addition

PHREEQC Coupled Kinetic Model of CO2 Outgassing amp Homogeneous Fe(II) OxidationmdashOak Hill Boreholes

pH FeII

Dissolved CO2 Dissolved O2 kLCO2a = 000001 s-1 kLO2a = 00012 s-1 kLO2a = 00007 s-1

kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1

Atmospheric equilibrium


kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated

CO2 Outgassing is Proportional to O2 Ingassing (model specifies first-order rates for outin gassing)

-d[C]dt = kLCamiddot([C] - [C]S) exponenBal asymptoBc approach to steady state

00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004

00002 kLa [O2] vs kLa [CO2]

1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

1stOrder CO2 outgassingrateconstant(1s)

New Iron Oxidation Rate Model for ldquoAMDTreatrdquo (combines abiotic and microbial oxidation kinetics)

The homogeneous oxidation rate law (Stumm and Lee 1961 Stumm and Morgan 1996) expressed in terms of [O2] and H+ (=10-pH) describes the abiotic oxidation of dissolved Fe(II)

-d[Fe(II)]dt = k1 middot[Fe(II)]middot[O2]middotH+-2

The heterogeneous oxidation rate law describes the catalytic abiotic oxidation of sorbed Fe(II) on precipitated Fe(III) oxyhydroxide surfaces where (Fe(III)) is the Fe(III) oxyhydroxide concentration expressed as Fe in mgL (Dempsey et al 2001 Dietz and Dempsey 2002)

-d[Fe(II)]dt = k2 (Fe(III)) middot[Fe(II)]middot[O2]middotH+-1

The microbial oxidation rate law describes the catalytic biological oxidation of Fe(II) by acidophilic microbes which become relevant at pH lt 5 (Pesic et al 1989 Kirby et al 1999)

-d[Fe(II)]dt = kbio middot Cbact middot[Fe(II)]middot[O2]middotH+

where kbio is the rate constant in L3mgmol2s Cbact is the concentration of iron-oxidizing bacteria in mgL (dry weight) [ ] indicates aqueous concentration in molL

New Iron Oxidation Rate Model for ldquoAMDTreatrdquomdash PHREEQC Coupled Kinetic Models of CO2 Outgassing

amp Fe(II) Oxidation Kinetic variables can be adjusted including CO2 outgassing and O2 ingassing rates plus abiotic and

DuraBon of aeraBon (Bme for reacBon) TimeSecs 28800is8hrs microbial FeII oxidation rates

Constants are temperature corrected CO2 outgassing rate in sec-1

Aer3 kLCO2a = 000056 s-1 Adjustment CO2 outgassing rate

Adjustment O2 ingassing rate (x kLaCO2) Aer2 kLCO2a = 000022 s-1

Adjustment abioBc homogeneous rate Aer1 kLCO2a = 000011 s-1

Adjustment abioBc heterogeneous rate Aer0 kLCO2a = 000001 s-1 Iron oxidizing bacteria microbial rate

Calcite saturaBon limit

Hydrogen peroxide added User may estimate Fe2 from Fe and pH Adjustment to H2O2 rate

plus TIC from alkalinity and pH And OpBon to specify FeIII recirculaBon specify H2O2 or recirculation of FeIII

Output includes pH solutes net acidity TDS SC and precipitated solids

mulBply Femg by 00090 to get [H2O2]

Estimated CO2 Outgassing amp O2 Ingassing Rate Constants for Various Treatment Technologies

kLa_20 = (LN((C1-CS)(C2-CS))t) (10241(TEMPC - 20)) where CisCO2 or O2

Fast

Slow

Fast

Slow

DissolvedO2 temperature and pH were measured using submersible electrodes DissolvedCO2 was computed from alkalinity pH and temperature data

Revised AMDTreat Chemical Cost Module mdash Caustic Titration with Pre-Aeration (Decarbonation)

PHREEQC Coupled Kinetic Models of CO2 Outgassing amp Fe(II) Oxidation

Original option for no aeration plus new option for kinetic pre-aeration (w wo hydrogen peroxide) that replaces original equilibrium aeration

Duration of pre-aeration in sec Dropdown kLa

CO2 outgassing rate constant in sec-1

Adjustment CO2 outgassing rate (x kLaCO2)

Adjustment O2 ingassing rate (x kLaCO2)

Hydrogen peroxide added

Adjustment to H2O2 rate Allows selection and evaluation of key Calcite saturation limit variables that affect chemical usage

efficiency


New Module For AMDTreat mdash PHREEQC Coupled Kinetic Models of CO2 Outgassing

amp Fe(II) Oxidation with Caustic Pre-Treatment Variable CO2 outgassing and O2OpBon to adjust iniBal pH with causBc

ingassing rates apply Can choose to adjust initial pH with caustic The required quantity of caustic is reported in units used by AMDTreat

CO2 outgassing rate

Adjustment CO2 outgassing rate


Adjustment abioBc homogeneous rate

Adjustment abioBc heterogeneous rate

Iron oxidizing bacteria Kinetic variables including CO2Calcite saturaBon limit outgassing and O2 ingassing rates plus Hydrogen peroxide added

Adjustment to H2O2 rate abiotic and microbial FeII oxidation rates can be adjusted by user In addition to caustic chemicals hydrogen peroxide and recirculation of FeIII

mulBply Femg by 00090 to get [H2O2] solids can be simulated

OpBon to specify FeIII recirculaBon

KINETICS OF LIMESTONE DISSOLUTION ndash pH CO2 and

SURFACE AREA EFFECTS

r = (k1bullaH+ + k2bullaH2CO3 + k3bullaH2O) - k4bullaCa2+bullaHCO3-

According to Plummer Wigley and Parkhurst (1978) the rate of CaCO3 dissolution is a function of three forward (dissolution) reactions CaCO3 + H+ rarr Ca2 + + HCO3

-

k1 CaCO3 + H2CO3 rarr Ca2 + + 2 HCO3 -

k2 CaCO3 + H2O rarr Ca2 + + HCO3 - + OH-

k3and the backward (precipitation) reaction Ca2 ++ HCO3 -rarrCaCO3+ H+

k4

Limestone Dissolution Rate Model for AMDTreat (ldquoPWPrdquo model emphasizes pH and CO2)

Although H+ H2CO3 and H2O reaction with calcite occur simultaneously the forward rate is dominated by a single species in the fields shown More than one species contributes significantly to the forward rate in the gray stippled area Along the lines labeled 1 2 and 3 the forward rate attributable to one species balances that of the other two

Limestone Dissolution Rate Model for AMDTreat (generalized expression corrects for surface area)

Appelo and Postma (2005) give a generalized rate expression for calcite dissolution that considers physical characteristics of the system as well as solution chemistry

R = k bull ( A V ) bull ( 1 ndash Ω )n

where A is calcite surface area V is volume of solution Ω is saturation state (IAPK = 10SIcc) and k and n are empirical coefficients that are obtained by fitting observed rates

For the ldquoPWPrdquo model applied to 1 liter solution the overall rate becomes

R = (k1bullaH+ + k2bullaH2CO3 + k3bullaH2O) bull ( A ) bull (1 - 10(n bull SIcc))

Plummer and others (1978) reported the forward rate constants as a function of temperature (T in K) in millimoles calcite per centimeter squared per second (mmolcm2s)

log k1 = 0198 ndash 444 T


log k3 = -586 ndash 317 T for T lt 298 log k3 = -110 ndash1737 T for T gt 298

Limestone Dissolution Rate Model for AMDTreat (surface area correction for coarse aggregate)

Plummer Wigley and Parkhurst (1978) reported unit surface area (SA) of 445 and 965 cm2gfor ldquocoarserdquoandldquofinerdquopar8clesrespec8vely used for empirical tes8ng and development of PWP rate model These SA values are 100 8mes larger than those for typical limestone aggregate Mul3ply cm2g by 100 gmol to get surface area (A) units of cm2mol used in AMDTreat rate model

New Module For AMDTreat mdash PHREEQC Kinetic Model of Limestone Dissolution

TimeSecs 7200is2hrs

Surface area cm2mol

Equilibrium approach

Mass available

MulBply surface area (SA) in cm2g by 100 to get SAcc in cm2mol

Calcite dissolution rate model of Plummer Wigley and Parkhurst (PWP 1978) Empirical testing and development of PWP rate model based on ldquocoarserdquo and ldquofinerdquo calcite particles with surface areas of 445 and 965 cm2g respectively

Surface area and exponential corrections permit application to larger particle sizes (045 to 144 cm2g) used in treatment systems

New Module For AMDTreat mdash PHREEQC Coupled Kinetic Models of Limestone

Dissolution amp Fe(II) Oxidation Rate models for calcite dissolution CO2 outgassing and O2 ingassing and FeII

Surface area

Equilibrium approach oxidation are combined to evaluate Mass available possible reactions in passive treatment

systems CO2 outgassing rate





Iron oxidizing bacteria Can simulate limestone treatment Calcite saturaBon limit

Hydrogen peroxide added followed by gas exchange and FeII Adjustment to H2O2 rate oxidation in an aerobic pond or aerobic

wetland or the independent treatment steps (not in sequence)

PHREEQC Coupled Kinetic Models Sequential Steps Limestone Dissolution + Fe(II) Oxidation

Pine Forest ALD + Aerobic Wetlands Sequential steps Variable detention times adjustable CO2 outgassing rates limestone surface area temperature and FeIII

Next slide

Can simulate passive treatment by anoxic or oxic limestone bed open (limestone) channels or spillways aerobic cascades ponds and wetlands

PHREEQC Coupled Kinetic Models Sequential Stepsmdash Pine Forest ALD + Aerobic Wetlands

Step Treatment 1 ALD 2 Riprap 3 Pond 4 Cascade 5 Wetland 6 Cascade 7 Wetland 8 Cascade 9 Wetland

0

1

2

7

3 4

5 6

8 9

PHREEQC Coupled Kinetic Models Sequential Steps Caustic + Limestone Dissolution + Fe(II) Oxidation

Silver Creek Aerobic Wetlands Sequential steps Pre-treatment with caustic andor peroxide and for each subsequent step variable detention times adjustable CO2 outgassing rates limestone surface area temperature and FeIII

Next slide

Can simulate active treatment including chemical addition or aeration or passive treatment including anoxic or oxic limestone bed open (limestone) channels or spillways aerobic cascades ponds and wetlands

PHREEQC Coupled Kinetic Models Sequential Stepsmdash Silver Creek Aerobic Wetlands

12

3

8

4 5

6 7

0

9

Step Treatment 1 Pond 2 Aeration 3 Pond 4 Aeration 5 Pond 6 Riprap 7 Wetland 8 Riprap 9 Wetland

 

 

 

 

Conclusions uuml Geochemical kinetics tools using PHREEQC have

been developed to evaluate mine effluent treatment options

uuml Graphical and tabular output indicates the pH and solute concentrations in effluent

uuml By adjusting kinetic variables or chemical dosing various passive andor active treatment strategies can be simulated

uuml AMDTreat cost-analysis software can be used to evaluate the feasibility for installation and operation of treatments that produce the desired effluent quality

Disclaimer Release Plans ldquoAlthough this software program has been used by the US Geological Survey (USGS) no warranty expressed or implied is made by the USGS or the US Government as to the accuracy and functioning of the program and related program material nor shall the fact of distribution constitute any such warranty and no responsibility is assumed by the USGS in connection therewithrdquo

uuml  FY2017 Development beta testing and review

uuml  FY2018 Official USGS ldquosoftware releaserdquo planned

uuml  httpswaterusgsgovsoftwarelistsgeochemical

uuml  FY2018 Incorporation of PHREEQC treatment simulations with AMDTreat to be released by OSMRE

uuml  httpamdosmregov

Questions uuml  Are the current models capable of simulating manganese (MnII)

oxidation kinetics

uuml  Can the models simulate the adsorption of cations by hydrous ferric oxides (HFO) as a kinetic process

uuml  Have you considered adsorption based rate models for the heterogeneous FeII and MnII oxidation kinetics

uuml  Does the limestone model consider changes in surface area of due to its dissolution or the accumulation of HFO coatings

uuml  Does the microbial FeII oxidation rate model consider oxidation by neutrophilic iron bacteria such as Gallionella or Leptothrix

uuml  What about the simulation of anaerobic processes in a BCR (Biochemical Reactor) and precipitation of metal sulfides

References Burrows JE Cravotta CA III Peters SC (2017) Enhanced Al and Zn removal from coal-mine drainage during rapid oxidation and precipitation

of Fe oxides at near-neutral pH Applied Geochemistry 78 194-210 Cravotta CA III (2003) Size and performance of anoxic limestone drains to neutralize acidic mine drainage Journal of Environmental Quality

32 1277-1289 Cravotta CA III (2015) Monitoring field experiments and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-

alkaline coal-mine drainage Pennsylvania USA Applied Geochemistry 62 96-107 Cravotta CA III Means B Arthur W McKenzie R Parkhurst DL (2015) AMDTreat 50+ with PHREEQC titration module to compute caustic

chemical quantity effluent quality and sludge volume Mine Water and the Environment 34 136-152 Davison W Seed G (1983) The kinetics of the oxidation of ferrous iron in synthetic and natural waters Geochimica et Cosmochimica Acta 47

67-79 Dempsey BA Roscoe HC Ames R Hedin R Byong-Hun J (2001) Ferrous oxidation chemistry in passive abiotic systems for the treatment of

mine drainage Geochemistry Exploration Environment Analysis 1 81-88 Dietz JM Dempsey BA (2002) Innovative treatment of alkaline mine drainage using recirculated iron oxides in a complete mix reactor

American Society of Mining and Reclamation 19th Annual Meeting p 496-516 Geroni JN Cravotta CA III Sapsford DJ (2012) Evolution of the chemistry of Fe bearing waters during CO2 degassing Applied Geochemistry

27 2335-2347 Kirby CS Elder-Brady JA (1998) Field determination of Fe2+ oxidation rates in acid mine drainage using a continuously-stirred tank reactor

Applied Geochemistry 13 509-520 Kirby CS Thomas HM Southam G Donald R (1999) Relative contributions of abiotic and biological factors in Fe(II) oxidation in mine

drainage Applied Geochemistry 14 511-530 Kirby CS Dennis A Kahler A (2009) Aeration to degas CO2 increase pH and increase iron oxidation rates for efficient treatment of net

alkaline mine drainage Applied Geochemistry 24 1175-1184 Langmuir D (1997) Aqueous environmental geochemistry Prentice Hall New Jersey USA 600 p (especially p 58-62) Parkhurst DL Appelo CAJ (2013) Description of input and examples for PHREEQC version 3mdashA computer program for speciation batch-

reaction one-dimensional transport and inverse geochemical calculations USGS Techniques Methods 6-A43 497 p Pesic B Oliver DJ Wichlacz P (1989) An electrochemical method of measuring the oxidation rate of ferrous to ferric iron with oxygen in the

presence of Thiobacillus ferrooxidans Biotechnology and Bioengineering 33 428-439 Plummer LN Wigley ML Parkhurst DL (1978) The kinetics of calcite dissolution in CO2-water systems at 5o to 60oC and 00 to 10 atm CO2

American Journal of Science 278 179-216 Rathbun RE (1998) Transport behavior and fate of volatile organic compounds in streams USGS Professional Paper 1589 151 p Singer PC Stumm W (1970) Acidic mine drainage the rate-determining step Science 167 121-123 Stumm W Lee GF (1961) Oxygenation of ferrous iron Industrial and Engineering Chemistry 53 143-146 Stumm W Morgan JJ (1996) Aquatic chemistry--chemical equilibria and rates in natural waters (3rd) New York Wiley-Interscience 1022 p

(especially p 682-691)

SOLUBILITY AND SORPTION CONTROL OF TRACE ELEMENTS

00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2

Solubilities of Metal Hydroxides

FeIII

MnIV

AlIII MnII FeII

FeIII amp MnIV ARE LEAST SOLUBLE OXIDATION RATE

IS LIMITING

METALS HAVE LOW

SOLUBLITY AT NEUTRAL TO ALKALINE pH

0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH

Schwertmannite x=175

Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase

Fe Limited by FeII-Carbonate and FeIII-Hydroxide and Sulfate Solubilities

FeII(OH)2

FeIICO3

FeIII(OH)3

FeIII8O8(OH)45(SO4)175

FeIIIOOH

Dissolved Fe is predominantly FeII

SORPTION OF CATIONS ON ldquoHFOrdquo 0

10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2

SORPTION OF ANIONS ON ldquoHFOrdquo 0

10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3

 

 

 

Summary Aqueous geochemical tools using PHREEQC have been developed by USGS for OSMRErsquos ldquoAMDTreatrdquo cost-analysis software

uuml Iron-oxidation kinetics model considers pH-dependent abiotic and biological rate laws plus effects of aeration rate on the pH and concentrations of CO2 and O2

uuml Limestone kinetics model considers solution chemistry plus the effects of surface area of limestone fragments

uuml Potential water quality from various treatments can be considered for feasibility and benefitscosts analysis

Al3+

Fe2+ Fe3+

Mn2+ Active Passive



Reactions slow


Low maintenance




High maintenance


PASSIVE TREATMENT

PASSIVE TREATMENT




Accumulation





eque

ncy i

n pe

rcen

t N=9

9 Fr

eque

ncy i

n pe

rcen

t N=4

1 40

35

30

25

20

15

10

5

0

40

35

30

25

20

15

10

5

0

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH field

pH lab (aged)


outgassing) HCO3

- = CO2 (gas) + OH-

Anthracite AMD

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH

pH field



Fe2+ + 025 O2 + 25 H2O rarr Fe(OH)3 + 2 H+

Bituminous AMD

AMDTreat



drainage)






 

 

 

 






 

 

 





AMDTreat 50+


St Michaels

Discharge

Escape PresentaBon

 

 






(1996)

(Kirby et al 1999)





Fe2+Fe(OH)2 0

Fe(OH)1+

Minutes Hours

Days

Months

Years













(summer 2013)



pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3

Al3+

Fe2+ Fe3+

Mn2+ Active Passive



Reactions slow


Low maintenance




High maintenance


PASSIVE TREATMENT

PASSIVE TREATMENT




Accumulation





eque

ncy i

n pe

rcen

t N=9

9 Fr

eque

ncy i

n pe

rcen

t N=4

1 40

35

30

25

20

15

10

5

0

40

35

30

25

20

15

10

5

0

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH field

pH lab (aged)


outgassing) HCO3

- = CO2 (gas) + OH-

Anthracite AMD

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH

pH field



Fe2+ + 025 O2 + 25 H2O rarr Fe(OH)3 + 2 H+

Bituminous AMD

AMDTreat



drainage)






 

 

 

 






 

 

 





AMDTreat 50+


St Michaels

Discharge

Escape PresentaBon

 

 






(1996)

(Kirby et al 1999)





Fe2+Fe(OH)2 0

Fe(OH)1+

Minutes Hours

Days

Months

Years













(summer 2013)



pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3


PASSIVE TREATMENT

PASSIVE TREATMENT




Accumulation





eque

ncy i

n pe

rcen

t N=9

9 Fr

eque

ncy i

n pe

rcen

t N=4

1 40

35

30

25

20

15

10

5

0

40

35

30

25

20

15

10

5

0

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH field

pH lab (aged)


outgassing) HCO3

- = CO2 (gas) + OH-

Anthracite AMD

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH

pH field



Fe2+ + 025 O2 + 25 H2O rarr Fe(OH)3 + 2 H+

Bituminous AMD

AMDTreat



drainage)






 

 

 

 






 

 

 





AMDTreat 50+


St Michaels

Discharge

Escape PresentaBon

 

 






(1996)

(Kirby et al 1999)





Fe2+Fe(OH)2 0

Fe(OH)1+

Minutes Hours

Days

Months

Years













(summer 2013)



pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3

PASSIVE TREATMENT




Accumulation





eque

ncy i

n pe

rcen

t N=9

9 Fr

eque

ncy i

n pe

rcen

t N=4

1 40

35

30

25

20

15

10

5

0

40

35

30

25

20

15

10

5

0

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH field

pH lab (aged)


outgassing) HCO3

- = CO2 (gas) + OH-

Anthracite AMD

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH

pH field



Fe2+ + 025 O2 + 25 H2O rarr Fe(OH)3 + 2 H+

Bituminous AMD

AMDTreat



drainage)






 

 

 

 






 

 

 





AMDTreat 50+


St Michaels

Discharge

Escape PresentaBon

 

 






(1996)

(Kirby et al 1999)





Fe2+Fe(OH)2 0

Fe(OH)1+

Minutes Hours

Days

Months

Years













(summer 2013)



pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3




eque

ncy i

n pe

rcen

t N=9

9 Fr

eque

ncy i

n pe

rcen

t N=4

1 40

35

30

25

20

15

10

5

0

40

35

30

25

20

15

10

5

0

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH field

pH lab (aged)


outgassing) HCO3

- = CO2 (gas) + OH-

Anthracite AMD

20 25 30 35 40 45 50 55 60 65 70 75 80 85

pH

pH field



Fe2+ + 025 O2 + 25 H2O rarr Fe(OH)3 + 2 H+

Bituminous AMD

AMDTreat



drainage)






 

 

 

 






 

 

 





AMDTreat 50+


St Michaels

Discharge

Escape PresentaBon

 

 






(1996)

(Kirby et al 1999)





Fe2+Fe(OH)2 0

Fe(OH)1+

Minutes Hours

Days

Months

Years













(summer 2013)



pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3

AMDTreat



drainage)






 

 

 

 






 

 

 





AMDTreat 50+


St Michaels

Discharge

Escape PresentaBon

 

 






(1996)

(Kirby et al 1999)





Fe2+Fe(OH)2 0

Fe(OH)1+

Minutes Hours

Days

Months

Years













(summer 2013)



pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3

 

 

 

 






 

 

 





AMDTreat 50+


St Michaels

Discharge

Escape PresentaBon

 

 






(1996)

(Kirby et al 1999)





Fe2+Fe(OH)2 0

Fe(OH)1+

Minutes Hours

Days

Months

Years













(summer 2013)



pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3

 

 






(1996)

(Kirby et al 1999)





Fe2+Fe(OH)2 0

Fe(OH)1+

Minutes Hours

Days

Months

Years













(summer 2013)



pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3


Fe2+Fe(OH)2 0

Fe(OH)1+

Minutes Hours

Days

Months

Years













(summer 2013)



pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3




(summer 2013)



pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3


pH FeII


kLCO2a = 000011 s-1 kLO2a = 000023 s-1

kLCO2a = 000022 s-1 kLO2a = 000002 s-1

kLCO2a = 000056 s-1



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3



kLCO2a = 000056 s-1

kLCO2a = 000011 s-1

kLCO2a = 000022 s-1

kLCO2a = 000001 s-1

Aerated

Not Aerated



00014

00012 y = 243x + 000

Rsup2 = 096 00010

00008

00006

00004


1stO

rder

O2 ingassingra

tecon

stan

t(1s)

00000 00000 00001 00002 00003 00004 00005 00006

























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3
























Fast

Slow

Fast

Slow











efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3










efficiency





CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3




CO2 outgassing rate













-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3





-




k4
















TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3














TimeSecs 7200is2hrs

Surface area cm2mol


Mass available






Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3



Surface area












Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3



Next slide




0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3



0

1

2

7

3 4

5 6

8 9



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3



Next slide



12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3


12

3

8

4 5

6 7

0

9


 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3

 

 

 

 













oxidation kinetics























00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3


















00000001

0000001

000001

00001

0001

001

01

1

10

100

1000

10000

100000

1000000

10000000

100000000

0 2 4 6 8 10 12 14

Con

cent

ratio

n M

e TO

T (m

gL)

pH

Al(OH)3

Fe(OH)3

Fe(OH)2

MnO2

Mn(OH)2

Cu(OH)2

Pb(OH)2

Ni(OH)2

Zn(OH)2

Co(OH)2

Cd(OH)2

Mg(OH)2

Ca(OH)2


FeIII

MnIV

AlIII MnII FeII


IS LIMITING

METALS HAVE LOW


0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3

0

2

4

6

8

10

12

14

16 2 4 6 8 10

-log

[Fe T

FeI

I amp F

eIII (

mol

L)]

pH

Fe(OH)3 (amorph)

Goethite FeOOH


Siderite FeCO3

Fe(OH)2

AMD140 [FeTOT]

Temp = 25oC pSO4

TOT

= 23 pK+ = 430 pCO2 = 20

Aqueous phase

Solid phase


FeII(OH)2

FeIICO3

FeIII(OH)3


FeIIIOOH



10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

Pb+2

CrIII

Cu+2

Zn+2

Cd+2

Co+2

Ni+2

Mn+2

Ba+2

Sr+2


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3


10

20

30

40

50

60

70

80

90

100 0

10

20

30

40

50

60

70

80

90

100

3 4 5 6 7 8 9 10 11

PER

CEN

T A

DSO

RB

ED

PER

CEN

T D

ISSO

LVED

pH

SO4-2

AsO4-3

SeO3-2

CrO4-2

PO4-3

Geochemical Modeling to Evaluate Remediation …...outgassing rate in -1sec Aer3: k a = 0.00056 s-1...

Documents

Transcript of Geochemical Modeling to Evaluate Remediation …...outgassing rate in -1sec Aer3: k a = 0.00056 s-1...