bench scale tests of selenium removal from mine waters raymond j. lovett* shipshaper, llp...
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Bench Scale Tests of Bench Scale Tests of Selenium Removal from Selenium Removal from
Mine WatersMine Waters
Raymond J. Lovett*Raymond J. Lovett*ShipShaper, LLPShipShaper, LLPMorgantown, WVMorgantown, WV
West Virginia Mine Drainage Task Force West Virginia Mine Drainage Task Force SymposiumSymposium
April 10-11, 2007April 10-11, 2007
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SupportSupport
National Mine Land Reclamation Center, National Mine Land Reclamation Center, West Virginia University, Paul ZiemkiewiczWest Virginia University, Paul Ziemkiewicz
United States Office of Surface MiningUnited States Office of Surface Mining
via OSM-WVU Cooperative Agreementvia OSM-WVU Cooperative Agreement
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ProblemsProblems
Overriding ConcernOverriding Concern The new regulatory limit is 5 ug/L.The new regulatory limit is 5 ug/L.
Specific ProblemsSpecific Problems Removing such low levels of SeRemoving such low levels of Se Differing chemistries of aqueous formsDiffering chemistries of aqueous forms
Selenate, SeOSelenate, SeO44-2-2, Se(VI), Se(VI)
Selenite, SeOSelenite, SeO33-2-2, Se(IV), Se(IV)
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Typical Southern West Virginia Typical Southern West Virginia Mine WaterMine Water
pH = 7.1pH = 7.1 [Se] = 13 ug/L[Se] = 13 ug/L [Fe] = 0.15 mg/L[Fe] = 0.15 mg/L [SO[SO44
-2-2]] = 980 mg/L= 980 mg/L Alkalinity = 235 mg/L as CaCOAlkalinity = 235 mg/L as CaCO33
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Selenium Removal Selenium Removal DifficultiesDifficulties
Different dissolved speciesDifferent dissolved species No direct precipitation chemistriesNo direct precipitation chemistries Reduction of selenate is difficultReduction of selenate is difficult Sulfate may interfereSulfate may interfere
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ObjectivesObjectives
Low installation costLow installation cost Removal to 5 ug/L or lessRemoval to 5 ug/L or less Low operating costLow operating cost PassivePassive
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Demonstrated ChemistriesDemonstrated Chemistries
Adsorption or co-precipitation by Adsorption or co-precipitation by Fe(III) hydroxides Fe(III) hydroxides
Reduction by Fe(0) Reduction by Fe(0) Reduction (adsorption) by Fe(II,III) Reduction (adsorption) by Fe(II,III)
mixed hydroxides (green rust)mixed hydroxides (green rust) Biological (bacterial Biological (bacterial
reduction/metabolism)reduction/metabolism)
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Reduction with Iron MetalReduction with Iron Metal
SeOSeO44-2-2 +Fe(0) => Fe(II,III) +Se(0) +Fe(0) => Fe(II,III) +Se(0)
SeOSeO33-2-2 +Fe(0) => Fe(II,III) +Se(0) +Fe(0) => Fe(II,III) +Se(0)
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Iron FormsIron Forms
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Apparatus 1Apparatus 1
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Operation, SideOperation, Side
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Operation, TopOperation, Top
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Iron AfterwardsIron Afterwards
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Selenium RemovalSelenium Removal
0
20
40
60
80
100
0 5 10 15 20 25
Selenium Total, ug/L
Selenium Dissolved, ug/L
Sel
eniu
m T
ota
l, u
g/L
Time (hrs)
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Exponential DecayExponential Decay
20
30
40
50
60
70
0 2 4 6 8 10 12 14
Se
len
ium
To
tal,
ug
/L
Time (hrs)
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Se Removal, 6-12 HoursSe Removal, 6-12 Hours
0
5
10
15
20
25
30
0 2 4 6 8 10 12 14
Se
len
ium
To
tal,
ug
/L
Time (hrs)
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Rate of Se RemovalRate of Se RemovalIntervalInterval ug Se/hrug Se/hr
0-1 hour0-1 hour 2424
0-8 hours0-8 hours 5.85.8
0-12 hours0-12 hours 4.94.9
6-12 hours6-12 hours 33
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Other ChangesOther ChangesTrial 1Trial 1
Time (hrs)Time (hrs) Iron (mg/L)Iron (mg/L) Manganese Manganese (mg/L)(mg/L)
00 <0.05<0.05 <0.01<0.01
2424 6.76.7 0.290.29
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Apparatus 2Apparatus 2
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Packed, beforePacked, before
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Packed, duringPacked, during
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Pipe FilterPipe Filter
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RecycleRecycle
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Selenium Removal 2Selenium Removal 2
0
10
20
30
40
50
60
70
0 2 4 6 8 10 12 14
Se
Co
nce
ntr
atio
n (
ug
/L)
Time (hrs)
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Other ChangesOther ChangesTrial 2Trial 2
Time (hrs)Time (hrs) Iron (mg/L)Iron (mg/L) Manganese Manganese (mg/L)(mg/L)
00 0.070.07 <0.01<0.01
2424 3.03.0 0.480.48
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Iron After Trial 2Iron After Trial 2
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Catenary Field SystemCatenary Field System
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Reduction with Iron MetalReduction with Iron Metal
PotentialPotential Removal of selenate and seleniteRemoval of selenate and selenite BarrierBarrier PassivePassive
ProblemsProblems Iron Oxides/ Dissolved Fe, MnIron Oxides/ Dissolved Fe, Mn ExhaustionExhaustion PassivationPassivation Expense (surface area)Expense (surface area)
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ConclusionsConclusions
Iron metal removes selenite and Iron metal removes selenite and selenate, but currently requires long selenate, but currently requires long contact timescontact times
Contact efficiency needs to be improvedContact efficiency needs to be improved
Iron and manganese release complicatesIron and manganese release complicates