pacific northwest national laboratory u.s. department of energy may 15, 2007 biogeochemistry of...

Pacific Northwest National LaboratoryUS Department of Energy

May 15 2007May 15 2007

Biogeochemistry of Technetium Discriminating Microscopic Abiotic and

Microbiologic Reaction Processes and Their Implications to Fate and Transport

Biogeochemistry of Technetium Discriminating Microscopic Abiotic and

Microbiologic Reaction Processes and Their Implications to Fate and Transport

J M Zachara1 S M Heald2 J K Fredrickson1 T Peretyazhko1 R Kukkadapu1 and M Marshall1

1Pacific Northwest National Laboratory Richland WA2Argonne National Laboratory and Advanced Photon Source Argonne IL

J M Zachara1 S M Heald2 J K Fredrickson1 T Peretyazhko1 R Kukkadapu1 and M Marshall1

1Pacific Northwest National Laboratory Richland WA2Argonne National Laboratory and Advanced Photon Source Argonne IL

2

AcknowledgementsAcknowledgements

OBERERSD - 5 years + support for Tc biogeochemistry

DOEORP and CH2M-Hill Hanford - Tank farm samples and characterization data

EMSL and APS user facilities

Alex Beliaev and Frank Loeffler ERSP project for Anaeromyxobacter culture and conditions

3

ERSDrsquos Long Term MeasureERSDrsquos Long Term Measure

ldquoBy 2015 provide sufficient scientific understanding to allow a

significant fraction of DOE sites to incorporate biological chemical

and physical processes into decision making for environmental

remediationrdquo

4

TechnetiumTechnetium

Fission product of 235Uranium

Exists in oxidation states +7 to -1

Highly mobile as Tc(VII) pertechnetate ion TcO4-

Biological activity high (sulphate analogue)

Microbial reduction to insoluble Tc(IV) (widespread)

235Uranium 99TechnetiumFission

T12 = 70 x 108 years

-emitter

21 x 105 years

-emitter

5

400 Ci of 99Tc was Released to the BC-Crib Area Where is it


CRIBS

Trenches

The SAC model forecasts that a growing plume of 99Tc should exist beneath the BC-cribs

99Tc 238ULithology

[Tc(VII)]max = 18x106 pCiL 10-6 molL

6

Different Scales ~ Different IssuesDifferent Scales ~ Different IssuesMolecular Microscopic Macroscopic Field

bull Bonding environment and local structure

bull Fundamental mechanisms

bull Energetics and structural controls

bull Solvation effects

bull Mineral residence phase identity amp composition

bull Reaction networks and kinetics

bull Morphologic and surface issues

bull Fundamental process coupling

bull Rate processesChemical MicrobiologicMass transfer

bull Advection effectsbull 1-D scaling issuesbull Pore scale process

coupling

bull Physical heterogeneityWater

velocitiesdirectionsReactants

bull Multi-scale mass transferbull Mixing amp averagingbull Distributed propertiesbull Seasonal issues (temperature precipitation)

7

Biogeochemical Cycles of Tc and Fe are LinkedBiogeochemical Cycles of Tc and Fe are Linked

Experimentsmeld environmentalmicrobiology geochemistryand mineralogy

Toolsbull Microscopyspectroscopybull X-ray diffraction and

scatteringbull Genomicsmutagenesisbull Controlled culture

Issuesbull Productsbull Mechanismsbull Kinetic controlsbull Indirect and direct

biologic effects

Impactsbull Weatheringbull Anoxic environmentsbull Contaminant behaviorbull Energy cycling

Fe(II)Fe(III) phases

Fe(III) oxides

Metal reducing organisms

abiotic reductants

Metal oxidizing organisms

abiotic oxidants

8

Solubility of TcO2Solubility of TcO2

TcO(OH)deg2(aq)

16784 pCiL

1678 pCiL

168 pCiL

Concentration of Tc(IV) fixed by solubililty at reduction pointDowngradient adsorption of Tc(IV) complexes or another reaction essential to reach MCL (900 pCiL)Adsorption behavior of TcO(OH)2deg(aq) unknown

MCL900 pCiL

Tc(VII)O4- + 4H+ + 3e- = Tc(IV)O2nH2O(s) + (2-n)H2O Eo = 0748 V

Tc(VII)O4- + 3Fe2+ + (n+7)H2O = Tc(IV)O2middotnH2O(s) + 3Fe(OH)3(s)+ 5H+

9

Technetium Redox Couples in Relation to Others at Standard State and pH = 7


-10 -5 0 5 10 15 20 pe

H2(g) H2O H2O O2(g)

NH4 ι NO3-

MnCO3 ι MnO2-

Fe(aq) ι Fe(OH3)2+

HS ι SO42-

Fe(aq) ι FeOOH2+

Hemes

Tc(IV)O2 ι Tc(VII)Tc(V)(VI) ι Tc(VII)

ldquoCH2Ordquo ι CO2(g)

reducing oxidizing

10

Complex Redox Chemistry of 3e- Transfer for Tc(VII)


Tc(VII)O4- + e- Tc(VI)O4

2- Tc(V) Tc(IV) [Tc(IV)OOHaq Tc(IV)O2nH2O(s)]

gelatin

rapid

tetrahedral tetrahedral octahedral

rapid

very

11

Disproportionation Rate Key to 3e- TransferDisproportionation Rate Key to 3e- Transfer

Tc(VII) Tc(VI) Fe(II) H+ log QK Gr

(molL) (kJmol)

100E-06 100E-12 0001 100E-07 26 14846100E-06 100E-13 0001 100E-07 16 9136100E-06 100E-14 0001 100E-07 06 3426100E-06 100E-15 0001 100E-07 -04 -2284100E-06 100E-16 0001 100E-07 -14 -7994100E-06 100E-17 0001 100E-07 -24 -13704

Reaction rate and extent increases with1 Disproportionation rate2 Concentration and redox potential of Fe(II)3 pH

Fe2+ + 3H2O + Tc(VII)O4- = Fe(III)(OH)3 + 3H+ + TcO4

2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12

Coupled Processes and ModelsCoupled Processes and Models

Reaction NetworkNecessary component reactions to define time evolution and steady stateComponent identities and concentrationsReaction parameters and dependencies

Coupled ProcessReactionMicrobiologic transformation (biogeochemical)Advectiondiffusion (water reactantproduct flux)Microbiologic speciation (ecologic)

13

Coupled ReactionsCoupled Reactions

Reaction Type Components Parameters

Electron transfer A + B rarr C + D Kdq=kfkb [A] [B] [X] [Y] [Z]Tc(VII)+Fe(II) = TcO22H2O+Fe(OH)3

Surface complexation B + E rarr F Ŝ [SOH]Fe(II)+FeOOH = Fe(II)-FeOOH

Electron transfer A + F rarr GTc(VII)+3Fe(II)-FeOOH rarr Tc(IV)-3Fe(III)Ox+FeOOH

Biological electron A + H rarr C biomass growth substrateTransfer specificity and kinetics

Tc(VII)+H2 = TcO2nH2O e-acceptordonor nutrients

Biologic reductive DE + J rarr B

FeOOHFe(OH3) + lactate = Fe(II) + CO2 + acetate

Aqueous complexation C + I rarr KTcO2nH2O + CO3

2- = TcOCO3(aq)

гbio

bio

г

14

Utilize dissolved and solid phase oxidized metals as electron acceptors for respiration when O2 becomes deplete

Strongly influence the composition and redox state of groundwaters and the valence state of polyvalent metals and radionuclides

Metal Reducing BacteriaMetal Reducing Bacteria

Bacterial mediation of geochemical reaction

Oxidized

Reduced

Oxidized

Reduced

Bacteria

Microorganisms mediate kinetically inhibited but thermodynamically favorable reactions

E for metabolism and growth

15

Kinetic Pathways for Tc(VII) Reduction and Tc(IV) Oxidation


Reduction (+ Fe(II) or MRB)

Tc(VII)O4-(aq)

Oxidation (+ O2 or MOB)

biologic (MRB)

+homogeneous

Fe(II)aq

heterogeneousFe(II)OH Fe(II)aq

Tc(IV)

bull speciationbull physical location

Fe(III) oxide

TcO4

t= kbio[ ] + khomo[ ] + khet1[ ] + khet2[ ]

Tc(IV)t

= kbio[ ] + khomo[ ] + khet1[ ] + khet2[ ]

medium

very slow

very fastmedium

16

Experimental Setup and Anoxic ChamberExperimental Setup and Anoxic Chamber

Glove box ldquoairrdquo is totally scrubbed of O2 using an oxygen trap based on heterogeneous reduction of O2 in Fe(II)Fe(OH)3 suspensions

lt 05 ppm

spectroscopypreparation

drying chamber

filtrationchamber

mineral and mineral-microbe

suspensions

oxygentrap

solids and liquid sampling

mineral solids and heterogeneous

precipitates

17

Probing Heterogeneous E-transferProbing Heterogeneous E-transfer

X-ray Adsorption Spectroscopy

57Fe-MossbauerSpectroscopy Combined Techniques

bull Valence statebull Local structurebull Tc-Obull Tc-Tcbull Tc-Fe

bull Valence bull Magnetic propertiesbull Bonding environmentbull Symmetry

APS EMSL In addition ndash HRTEM (EMSL)

(looking at Tc) (looking at Fe)

hFe 56Fe Al

57Fe h

57Fe

SO-Fe(II)OH + Tc(VII) rarr Г =

Heterogeneous Reduction of Pertechnetate [Tc(VII)O4

-] by Surface Complexed Fe(II) at pH = 7Heterogeneous Reduction of Pertechnetate

[Tc(VII)O4-] by Surface Complexed Fe(II) at pH = 7

Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days

+ FeOOH + Tc(VII)+ FeOOH

+ Tc(VII)

-6 to -2 day Fe(II)aq

-2 to 0 day FeO-Fe(II)OH0 day + FeO-Fe(II)OH+Tc(IV)Fe(III)

Issuesbull Stoichiometry of Fe(III) and Tc(IV)bull Nature of Fe(III) and Tc(IV) phasesbull Location and association of Fe(II)bull Speciation effects on heterogeneous

oxidation

3FeO-Fe(II)OH + Tc(VII)O4- = 3FeO-Fe(III)OH2 [] + Tc(IV)O2H2O []

19

Products of Heterogeneous Tc(VII)O4- Reduction

by Fe(II) on Goethite Products of Heterogeneous Tc(VII)O4

- Reduction by Fe(II) on Goethite

k A-1 R Aring

What is Fe(III)Tc(IV)Ox Where is readsorbed Fe(II)

56Fe- goethite(Moumlssbauer invisible)

57Fe(II)(Moumlssbauer visible)

bull Magnetic order and peak positions consistent with Fe(III) and goethite

bull No Fe(II)

bull ldquotwordquo Fe(II) sites

bull Spectra before Tc(IV) addition almost identical

20

Many Metal-Reducing Bacteria Change the Valence of Pertechnetate [Tc(VII)]


2CP-C

Biogenic TcO2nH2O shows less Tc-Tc second neighbors and different long range order

Consistent with small size (2-3 nm) of biogenic precipitates

Tc-O

Tc-Tc

Tc-OTc-Tc

21

HRTEM of TcO2H2O Precipitates on and within CN32 S putrefaciens


ΔG = 23 S

log Kso(s) = log Kso(s=o) +


⅔23 RT

S

⅔23 RT

Md

Small biogenic precipitates are more soluble (eg 10-7 molL)

22

Biogenic Products of Dissimilatory Iron Reduction are Reactive and Significant to

Trace Element Cycling



Fe2+(aq) helliphelliphelliphelliphelliphelliphelliphelliphellip reductant of Cr(VI)

and other dissolved oxidants

-FeOOH helliphelliphelliphelliphelliphelliphelliphelliphellip reactive crystalline Fe(III) oxide

-Fe(II) helliphelliphelliphelliphelliphelliphelliphelliphellip facile reductant of chlorinatedsolvents nitroaromatics U(VI)Tc(VII) Cr(VI) etc

FeCO3helliphelliphelliphelliphelliphelliphelliphelliphellip reversible repository of

divalent metals Co Zn Ni Cd

Fe3O4helliphelliphelliphelliphelliphelliphelliphelliphellip irreversible repository of divalent

metals Zn Ni Co heterogeneousreductant

[FeII(6-x)FeIII

x(OH)12] helliphellip unique anion exchanger withX+[(A2-)x2bullyH2O]x- reductant properties

Products Implications

aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII

x(OH)12] x+[(A2-)x2bullyH2O]x-

Implications

reductant of Cr(VI)and other dissolved oxidants

facile reductant of chlorinatedsolvents nitroaromatics U(VI)Tc(VII) Cr(VI) etc

reversible repository ofdivalent metals Co Zn Ni Cd

irreversible repository of divalentmetals Zn Ni Co etc

unique anion exchangerwith reductant properties

SP980200235

+ DIRB

Starting Oxide

2LFH

23

Experiments to Assess Abiotic and Biotic Reaction Predominance

Tc and 2LFH Behavior in Anoxic Suspensions with MR-1 and H2 or Lactate



ID Experiment Product [Tc]aq

[Tc(IV]aq

Start 300x10-4

3 Tc(IV)-2LFH+Fe(II) ~70 goe 20 mag lt15x10-9

4 Tc(IV)-2LFH+AH2DS nanomagnetite 184x10-9

5 bio-Fe3O4+Tc(VII) 60 nm magnetite 193x10-9

6 Tc(VII)+MR-1+H2 TcO2nH2O 152x10-7

10 2LFH+Tc(VII)+MR-1+H2 large particle goethite 343x10-8

12 2LFH+Tc(VII)+MR-1+lactate 5LFH 378x10-6

499x10-7

14 Tc(IV)-2LFH+MR-1+H2 large particle goethite 411x10-8

15 Tc(IV)-2LFH+MR-1+lactate 5LFH 412x10-6

276x10-7

Hypothesis H2 would promote microbiologic reduction


[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24

What Reductive Process Dominates in Mineral-Microbe Suspension


MR-1

H2

Products display different EXAFS spectra from abiotic and biotic TcO2

Aqueous concentration tracks speciation and mineralogy

2-line ferrihydrite + Tc(VII)aq + MR-1 -FeOOH + Fe-O-Fe(II)OH + Tc(IV)(s)[]timeFe(II)

Tc-O

Tc-Tc

Tc-Fe

25

Biomineralization Products and Tc Concentrations with Shewanella Anaeromyxobacter and GeobacterBiomineralization Products and Tc Concentrations

with Shewanella Anaeromyxobacter and Geobacter

Reactants Product [Tc] [Fe(II)]-

05NHCl

(mol L-1)

2LFH + Tc(VII) + MR-1 + H2 rarr goethite 49x10-9 169x10-3

2LFH + Tc(VII) + CN-32 + H2 rarr goethite ge magnetite 81x10-9 336-x10-3

2LFH + Tc(VII) + 2CP-C + H2 rarr poorly crystalline goethite 117x10-8 264x10-3

2LFH + Tc(VII) + PCA + H2 rarr well crystalline goethite amp magnetite 849x10-9 312x10-3

Tc(VII) + PCA + H2 rarr TcO2nH2O 179x10-7[TcToT] = 302x10-4 [FeToT] = 302x10-2

26

XAS of Ferrihydrite Incubated with H2 and Various MRB


Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)

heterogeneousreductionsignature

MR-1 CN32 ndash Shewanella2CP-C ndash AnaeromyxobacterPCA - Geobacter

27

EXAFS Interpretation Involves Various Tc(IV)O2 Models


Long chains Abiotic and biotic TcO2nH2O

Dimers and trimers coordinated to Fe-O with diffuse Fe scattering Sorbed Fe(II) on phyllosilicates (FRC)

Monomers and dimers coordinated to Fe-O with more intense Fe scattering Homogeneous Tc(IV) heterogeneous Tc(IV) on goethitehematite diasporecorundum and magnetite biotransformation products of ferrihydrite and Tc(IV)-ferrihydrite

Tc-TcTc-Fe

Dimeric surface complex

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28

Interfacial Speciation of both Tc and Fe Influence Oxidation Rate


Time hrs

T

c O

xidi

zed

Abiotic lt BioticH2 lt Bioticlactate lt TcO2nH2O

Tc(IV)(s) + O2(aq) rarr Tc(VII)(aq)

29

ConclusionsConclusions

Electron donor has a major role because of effects on enzymology and TcFe Lactate-enhances Fe(III) reduction slows Tc(VII) reduction and

complexes Tc(IV) H2 ndash stimulates Tc(VII) reduction and slows Fe(III) reduction

Heterogeneous Tc(VII) reduction predominates in Fe(III) oxide-microbe systems

Slower rates of heterogeneous reduction in phyllosilicate dominated systems may allow microbiologic reduction to predominate

Tc(VII) speciation varies in octahedra chain length Relatively insensitive to biogenic mineral phase Sensitive to apparent respiration rate and Fe(II) location

Tc(IV) oxidation rates slowed by mineral association difficult to interpret

30

Evolving Hydrology at HanfordEvolving Hydrology at Hanford

groundwater mounding fromSurface water discharge

W to E flowpath to Columbia River

bull Fast flowbull Contaminants migrate in

oxic layerbull Homo- or

heterogeneous reduction minimal

bull Tc(VII) migrates to Columbia


dep

th

dO2

dep

th

dO2

Past

Futurebull Slower flowbull Aerobic respiration

depletes O2 anaerobic sites

bull Mineral solubilization of Fe(II) heterogeneous reductants

bull Tc(VII) migration is retarded

high O2River water

31

Historic Releases of Processes Waters at Hanford Have Strongly Influenced Groundwater Composition

These will change in the future



32

Secondary Fe(II)-Rich Saponite Results as a Weathering Product of Ferrous-Silicate Glass

in Basaltic Lithic Fragments



Fe(II)-glass Fe(II)OH

Fe(II)aq

33

57Fe Moumlssbauer Spectroscopy of Hanford Sediments


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7

Experimental Simulated Phyllosilicate Fe(III) 8Phyllosilicate Fe(II) 17Clinochlore 6 7Mag-Fe(III) 8Mag-Fe(II)Fe(III) 5Goethite 47Hematite 2

-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101

Bulk SampleMagnetic fraction

Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34

Future Research DirectionsFuture Research Directions

Focused on Tc-biogeochemistry in Hanford subsurface sediments and effects of the globally falling water table (lower O2 and slower flow rates)

Based on the observation that sorbed Fe(II) on certain surfaces is a strong reductant for Tc(VII) even when aqueous Fe(II) is near DL

Emphasizes effects of O2 consumption by indigenous microbes and ferrous-containing mineral solids on Fe(II) solubility surface complexed Fe(II) and in-situ heterogeneous Tc(VII) reduction

Will incorporate aquifer sediments along a flow-path from 200 A plateau to Columbia River

Involves laboratory studies with Hanford aquifer sediments (microbial ecology mineralogy biogeochemistry) and field experiments in pristine and Tc(VII)-contaminated groundwater plumes

35

Summary RemarksSummary Remarks

Basic ScienceBiotic and abiotic processes can leave distinct signatures at the molecular and microscopic level that allow process discrimination Unraveling bioticabiotic process coupling allows for understanding of non-linear combined effects less empiricism and improved extrapolation to other systemsProcess predominance strongly dependent on fundamental system parameters eg mineralogy and surface area respiration and metabolic rate that are conducive to modeling

HanfordIdentifying natural attenuation mechanisms and their rate and effectQuantifying biogeochemical processes that can reduce [Tc(VII)] to required regulatory needs (eg lt 10-9 molL)Bounding constraints imposed by natural processes as the site evolves in response to system changes

Contributions to ERSDs Long Term MeasureQuantifying coupled process effects that dominate fate and transport for some radionuclidesDevelopment of modelsparameters of appropriate phenomenology and complexitySupport decisions on need and approach for remediation

Slide 1

Heterogeneous Reduction of Pertechnetate [Tc(VII)O4-] by Surface Complexed Fe(II) at pH = 7

2

AcknowledgementsAcknowledgements

OBERERSD - 5 years + support for Tc biogeochemistry

DOEORP and CH2M-Hill Hanford - Tank farm samples and characterization data

EMSL and APS user facilities

Alex Beliaev and Frank Loeffler ERSP project for Anaeromyxobacter culture and conditions

3





remediationrdquo

4








T12 = 70 x 108 years

-emitter

21 x 105 years

-emitter

5



CRIBS

Trenches


99Tc 238ULithology


6












coupling




7






biologic effects



Fe(III) oxides


abiotic reductants


abiotic oxidants

8


TcO(OH)deg2(aq)

16784 pCiL

1678 pCiL

168 pCiL


MCL900 pCiL



9



-10 -5 0 5 10 15 20 pe

H2(g) H2O H2O O2(g)

NH4 ι NO3-

MnCO3 ι MnO2-

Fe(aq) ι Fe(OH3)2+

HS ι SO42-

Fe(aq) ι FeOOH2+

Hemes



reducing oxidizing

10





gelatin

rapid


rapid

very

11



(molL) (kJmol)




2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


3





remediationrdquo

4








T12 = 70 x 108 years

-emitter

21 x 105 years

-emitter

5



CRIBS

Trenches


99Tc 238ULithology


6












coupling




7






biologic effects



Fe(III) oxides


abiotic reductants


abiotic oxidants

8


TcO(OH)deg2(aq)

16784 pCiL

1678 pCiL

168 pCiL


MCL900 pCiL



9



-10 -5 0 5 10 15 20 pe

H2(g) H2O H2O O2(g)

NH4 ι NO3-

MnCO3 ι MnO2-

Fe(aq) ι Fe(OH3)2+

HS ι SO42-

Fe(aq) ι FeOOH2+

Hemes



reducing oxidizing

10





gelatin

rapid


rapid

very

11



(molL) (kJmol)




2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


4








T12 = 70 x 108 years

-emitter

21 x 105 years

-emitter

5



CRIBS

Trenches


99Tc 238ULithology


6












coupling




7






biologic effects



Fe(III) oxides


abiotic reductants


abiotic oxidants

8


TcO(OH)deg2(aq)

16784 pCiL

1678 pCiL

168 pCiL


MCL900 pCiL



9



-10 -5 0 5 10 15 20 pe

H2(g) H2O H2O O2(g)

NH4 ι NO3-

MnCO3 ι MnO2-

Fe(aq) ι Fe(OH3)2+

HS ι SO42-

Fe(aq) ι FeOOH2+

Hemes



reducing oxidizing

10





gelatin

rapid


rapid

very

11



(molL) (kJmol)




2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


5



CRIBS

Trenches


99Tc 238ULithology


6












coupling




7






biologic effects



Fe(III) oxides


abiotic reductants


abiotic oxidants

8


TcO(OH)deg2(aq)

16784 pCiL

1678 pCiL

168 pCiL


MCL900 pCiL



9



-10 -5 0 5 10 15 20 pe

H2(g) H2O H2O O2(g)

NH4 ι NO3-

MnCO3 ι MnO2-

Fe(aq) ι Fe(OH3)2+

HS ι SO42-

Fe(aq) ι FeOOH2+

Hemes



reducing oxidizing

10





gelatin

rapid


rapid

very

11



(molL) (kJmol)




2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


6












coupling




7






biologic effects



Fe(III) oxides


abiotic reductants


abiotic oxidants

8


TcO(OH)deg2(aq)

16784 pCiL

1678 pCiL

168 pCiL


MCL900 pCiL



9



-10 -5 0 5 10 15 20 pe

H2(g) H2O H2O O2(g)

NH4 ι NO3-

MnCO3 ι MnO2-

Fe(aq) ι Fe(OH3)2+

HS ι SO42-

Fe(aq) ι FeOOH2+

Hemes



reducing oxidizing

10





gelatin

rapid


rapid

very

11



(molL) (kJmol)




2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


7






biologic effects



Fe(III) oxides


abiotic reductants


abiotic oxidants

8


TcO(OH)deg2(aq)

16784 pCiL

1678 pCiL

168 pCiL


MCL900 pCiL



9



-10 -5 0 5 10 15 20 pe

H2(g) H2O H2O O2(g)

NH4 ι NO3-

MnCO3 ι MnO2-

Fe(aq) ι Fe(OH3)2+

HS ι SO42-

Fe(aq) ι FeOOH2+

Hemes



reducing oxidizing

10





gelatin

rapid


rapid

very

11



(molL) (kJmol)




2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


8


TcO(OH)deg2(aq)

16784 pCiL

1678 pCiL

168 pCiL


MCL900 pCiL



9



-10 -5 0 5 10 15 20 pe

H2(g) H2O H2O O2(g)

NH4 ι NO3-

MnCO3 ι MnO2-

Fe(aq) ι Fe(OH3)2+

HS ι SO42-

Fe(aq) ι FeOOH2+

Hemes



reducing oxidizing

10





gelatin

rapid


rapid

very

11



(molL) (kJmol)




2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


9



-10 -5 0 5 10 15 20 pe

H2(g) H2O H2O O2(g)

NH4 ι NO3-

MnCO3 ι MnO2-

Fe(aq) ι Fe(OH3)2+

HS ι SO42-

Fe(aq) ι FeOOH2+

Hemes



reducing oxidizing

10





gelatin

rapid


rapid

very

11



(molL) (kJmol)




2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


10





gelatin

rapid


rapid

very

11



(molL) (kJmol)




2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


11



(molL) (kJmol)




2- log K = 266

Tc(VII)Tc(V)

Tc(IV)

12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


12




13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


13











2- = TcOCO3(aq)

гbio

bio

г

14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


14





Oxidized

Reduced

Oxidized

Reduced

Bacteria



15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


15




Tc(VII)O4-(aq)


biologic (MRB)

+homogeneous

Fe(II)aq


Tc(IV)


Fe(III) oxide

TcO4


Tc(IV)t


medium

very slow

very fastmedium

16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


16



lt 05 ppm


drying chamber

filtrationchamber


suspensions

oxygentrap



precipitates

17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


17








hFe 56Fe Al

57Fe h

57Fe





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1





Dis

so

lved

Tc(

VII

)

mo

l L

-1

Dis

so

lved

Fe(

II)

mm

ol

L-1

To

tal

Fe

(II)

m

mo

l L

-1

Time daysTime days

Time days


+ Tc(VII)




oxidation


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


19




k A-1 R Aring





bull No Fe(II)



20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


20



2CP-C



Tc-O

Tc-Tc

Tc-OTc-Tc

21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


21



ΔG = 23 S



⅔23 RT

S

⅔23 RT

Md


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


22













[FeII(6-x)FeIII



aa

Starting Oxide

HFO

FeOOH + DIRB

Fe2O3

Products

Fe2+(aq)

Fe(ll)

FeCO3

Fe3O4

[FeII(6-x)FeIII


Implications






SP980200235

+ DIRB

Starting Oxide

2LFH

23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


23






[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7



[Tc(IV]aq

Start 300x10-4







499x10-7



276x10-7


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


24



MR-1

H2




Tc-O

Tc-Tc

Tc-Fe

25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


25




05NHCl

(mol L-1)






26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


26



Tc-O(ts)

Tc-Fe (ss)

Tc-Tc (ss)

Tc-O (fs)



27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


27






Tc-TcTc-Fe


Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

Tc(IV) Tc(IV)

H2O

H2O

Fe(III)

H2O

HO

HO

H2O

Fe(III)

Fe(III)

[Tc]aq

28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


28



Time hrs

T

c O

xidi

zed



29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


29








30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


30









dep

th

dO2

dep

th

dO2

Past





high O2River water

31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


31





32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


32






Fe(II)aq

33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


33



Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


Velocity (mms)

-12 -9 -6 -3 0 3 6 9 12

Inte

nsity

(a

u)

124e+7

126e+7

128e+7

130e+7

132e+7


-12 -9 -6 -3 0 3 6 9 12

T

rans

mis

sion

93

94

95

96

97

98

99

100

101


34







35





Slide 1


34







35





Slide 1


35





Slide 1


pacific northwest national laboratory u.s. department of energy may 15, 2007 biogeochemistry of...

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