Jon Smoyer P.G., PA Department of Environmental Protection (DEP), “Hydrogen Peroxide- Review of its Role as Part of a Mine Drainage Treatment Strategy” Hydrogen Peroxide has been used to oxidize and remove ferrous iron from mine drainage for decades. It is a relatively inexpensive and effective oxidant that can be used to achieve rapid ferrous iron oxidation in many active and semi-passive mine drainage treatment systems. This presentation outlines the physical properties, concentrations, and available delivery options for hydrogen peroxide.

1. Hydrogen Peroxide- Review of its Role as
Part of a Mine Drainage Treatment
Strategy
Jon Smoyer, PG August 9, 2013
Bureau of Abandoned Mine Reclamation

2. • What is Hydrogen Peroxide?
• Chemically – H202 - only one atom of oxygen
different than water but….
• DO NOT BE FOOLED. HYDROGEN
PEROXIDE IS A VERY POWERFUL
OXIDANT AND IF NOT RESPECTED, CAN
BE A VERY DANGEROUS CHEMICAL TO
MOST LIVING ORGANISMS

3. Physical and chemical properties
Hydrogen peroxide is a clear, colorless, non-flammable liquid. It has a slightly
pungent odor. Hydrogen peroxide is a versatile chemical with a wide variety of
applications. It is commercially available as aqueous solution in various
concentrations and grades.
Parameter units H2O2 concentration
Content % by wt. 30 35 50 60 70 87
Content g H2O2 100%/kg 300 350 500 600 700 870
Content g H2O2 100%/l 333 396 598 745 902 1197
Content Mol % 18.5 22.2 34.6 44.3 55.3 78.0
Active oxygen
content
% by wt. 14.1 16.5 23.5 28.2 32.9 40.9
Density at
20 °C
g/cm³ 1.111 1.132 1.196 1.241 1.288 1.376
Freezing point2) °C -26 -33 (-27F) -52 (-62F) -56 -40 -16
Boiling point
(normal pressure)3) °C 106 108 114 119 125 139

4. • TYPICALLY AVAILABLE IN 35% OR 50% IN,
DRUMS, TOTES OR IN BULK DELIVERY.
• BULK DELIVERY PREFERRED FOR ANY TYPE OF
LONG TERM TREATMENT.
• 50% OBVIOUSLY MORE COST EFFECTIVE

5. HYDROGEN PEROXIDE WHEN REACTED BREAKS
DOWN INTO WATER AND OXYGEN. NO
BYPRODUCTS OR RESIDUES OTHER THAN THOSE
LEFT BY THE REACTANT THAT WAS OXIDIZED.
NO INCREASE IN TOTAL DISSOLVED SOLIDS.

6. • AMD REACTION WITH HYDROGEN PEROXIDE
• 2 Fe +2 + H2O2 + 4 OH-
2Fe (OH)3 (precip.)
Reaction consumes
alkalinity (or liberates
mineral acidity)

7. • Hydrogen Peroxide is a non-discriminant
oxidizer. It will oxidize anything that happens
to be in the AMD stream. However, in most
cases, the iron is the first available reactive
element that will precipitate in large
quantities.
• Iron will continue to precipitate until the
solubility point of the isotope of Fe is attained
by the pH and/or Eh of the solution.

9. PA DEP WILDWOOD TREATMENT SYSTEM
SINCE 1978

10. • Why use hydrogen peroxide?…
• Much more efficient than atmospheric aeration.
Oxidation with atmosphere is limited by the fact that
air is only 20% oxygen and the exchange of this limited
oxygen into water is slow and relatively inefficient.
• Can be more cost effective than adding alkaline
material to AMD in order to adjust the solubility of the
solution. Oxidize as raw, rather than adjust pH to bring
the iron out of solution. This avoids the inefficiencies
of lime dissolution and therefore makes less sludge.

11. • BENCH SCALE TESTS ON NEAR ALKALINE –
IRON TYPE AMD (MEANS AND BEAM, 2011)
• BUCKET/ BENCH SCALE TESTS WERE
PERFORMED ON DISCHARGES THAT WERE
NEAR ALKALINE CONDITIONS (SOME WERE
INFACT NET ACIDIC) THAT WERE OF LARGE
VOLUME AND LIMITED SPACE SUCH THAT
PURELY PASSIVE TREATMENT WOULD BE
UNLIKELY

12. • CRABTREE DISCHARGE (WESTMORELAND CO.)
Lab pH
Lab
Alkalinity TIC SC TSS Al - D Al - T Ca - D Ca - T Fe - D Fe - T
Raw 6.1 152.4 46.4 1482 8 0.459 1.108 154.3 149.6 59.62 58.89
H2O2 + 16 hrs 5.8 53.4 24 1453 5 0.2 0.2 142 148 0.02 1.26

13. • CRABTREE DISCHARGE (WESTMORELAND CO.)
CONT.
K - D K - T Mg - D Mg - T Mn - D Mn-T Na - D Na - T Si - D Si - T Zn - D Zn - T Nitrate SO4 Cl-
Hot
Acidity
Raw 3.723 3.8 49.9 53.3 2.23 2.26 106.7 106.5 23.88 23.84 0.084 0.088 0.06 681.0 71.0 -24.4
H2O2 +16
HRS 4.211 4.3 48.6 51.3 2.14 2.23 95.8 98.8 18.68 20.65 0.087 0.088 0.07 627.4 70.5 -34

14. • HOFFMAN RUN DISCHARGE (SOMSERSET CO.)
Lab
pH
Lab
Alk SC TSS Al - D Al - T Ca - DCa - T Fe - D Fe - T
Raw 5.9 66.2 910 6 0.2 0.2 92.6 93.6 47.5 48.5
H2O2 +
30 min 3.9 0 920 68 0.2 0.2 94.7 94.7 0.636 26.5
H2O2 +
16 hrs 3.9 0.6 876 5 0.2 0.2 88.6 91.3 0.288 1.93

15. • HOFFMAN RUN DISCHARGE (CONT.)
K -
D
K -
T
Mg -
D
Mg -
T
Mn
- D
Mn-
T
Na -
D
Na -
T
Si -
D Si - T Zn - DZn - T SO4 Cl-
Hot
Acidity
RAW 2.6 2.7 50.7 51.7 7.9 8.1 2.9 2.9 8.0 8.2 0.076 0.078 356.8 3 27
H2O2
+30
MIN 2.6 2.6 51.6 54.2 7.9 8.0 2.7 2.8 7.9 8.1 0.082 0.076 403.52.6 40.6
H2O2 +
16 HRS 2.4 2.6 50.5 52.4 7.6 8.1 2.5 2.7nd nd 0.077 0.086 447.63.3 18

16. • ST. MICHAEL DISCHARGE (CAMBRIA CO.)
Lab pH
Lab
Alk TIC SC
TDS @
105 TSS Al - D Al - T
Ca -
D Ca - T Fe - DFe - T
Raw 5.8 46.6 31.8 1631 1704 14 1.56 2.81 203 205 132 133
H2O2
+ 10
MIN 3.0 0 31 1934 1484 252 2.5 2.24 207 213 47.8 137
H2O2
+ 5HRS 3.0 0 24.6 1925 1540 32 2.24 2.29 204 207 30.8 41.2

17. • GLADDEN DISCHARGE (ALLEGHENY CO.)
Lab pH
Lab
Alk TIC SC
TDS @
105 TSS Al - D Al - T Ca - DCa - T Fe - D Fe - T
Raw 6.2 151.8 79.5 1741 1348 5 0.2 0.243 86.3 89.5 86 89.5
H2O2 +
3MIN 5.1 24.8 63.5 1725 1280 184 0.2 0.262 86.3 89.8 0.488 91.9
H2O2 +
18 MIN 5.0 22 62 1722 1256 50 0.2 0.2 87.6 89.4 0.039 26.9
H2O2 +
2HRS
18MIN 5.1 21.6 42.5 1726 1258 14 0.2 0.2 85.4 88.8 0.02 6.425

18. • LTV Banning and Mon-View Mathies -Recent
financial market condition has affected trust
revenue generation
• PADEP (Beam et. al.) with the assistance of OSM
(Means) formed evaluation team to perform cost-
reduction evaluations
• Evaluation team focused on reducing annual
operation and chemical costs
LTV TREATMENT SYSTEM EVALUATIONS

19. • LTV TREATMENT COST EVALUATION
5-Step Approach
1. Determine current dosing rates;
2. Quantify consumption of alkali chemical;
3. Develop alternative treatment strategies;
4. Pilot test alternative strategies;
5. Perform cost and performance comparison
evaluation

20. Step 1: Quantify original Mon-View NaOH Costs
20% NaOH Dosing = 122 gal/day = $116/day = $42,340/yr
Sample Location
Flow
(gpm)
Field
pH
Field
Alkalinity
Ca - D Ca - T Fe - D Fe - T Na - D Na - T
Reaction tank Influent 396 6.86 400 96.5 100 34.8 46.3 448 468
Reaction tank Effluent 396 7.22 385 95.5 102 4.306 46.2 475 515
Final Effluent 396 7.48 375 94.3 97.2 1.1 1.09 454 502
All values in mg/L, Alkalinity = mg/L as CaCO3, D = Dissolved, T = Total
Mon-View: Results of Original 20% Sodium Hydroxide (w/w) Treatment Configuation

21. Step 1: Quantify Banning Hydrate Costs
Hydrated Lime Dosing = 3.77 tons/day = $603/day = $220,168/yr
Sample Location
Flow
(gpm)
Field
pH
Field
Alkalinity
Ca - D Ca - T Fe - D Fe - T Na - D Na - T
Reaction tank Influent 2310 6.89 394 114 112 18 18.0 434 432
Reaction tank Effluent 2310 8.28 310 87.5 256 0.026 16.9 440 444
Final Effluent 2310 8.25 306 71.5 92 <.020 1.0 390 462
All values in mg/L, Alkalinity = mg/L as CaCO3, D = Dissolved, T = Total
Banning : Results of Original Hydrated Lime Treatment Configuation

22. 1. Fe(II) Removal
 Fe2+ + 2OH- = Fe(OH)2
 Fe2+ + .5H2O + .25O2 + 2OH- = Fe(OH)3
STEP 2: Quantify Sources of Alkali Consumption
2. Calcite Formation
 Dissolved-precipitate
Ca2+ + OH- + CO2(aq) = CaCO3(s) + H+
 Recarbonation
Ca(OH)2(s) + CO2(aq) = CaCO3(s) + H2O

23. Mechanism for Hydrate Consumption
Hydroxylation - Reaction with OH- ion with aqueous
species to form H2O and other species
– Hydroxylation of anion
HCO3
- + OH- = CO3
2- + H2O
– Hydroxylation of cation
Mg2+ + OH- = MgOH+
– Hydroxylation of Aqueous complexes
CaHCO3
+ + OH- = CaCO3(aq) + H2O

24. Daily Consumption of NaOH at Mon-View
$53
$58
$5
Hydroxylation
Fe Removal
Calcite Formation

25. Using pH adjustment as a treatment strategy is costing $561/day
worth of nuisance consumption to treat 18 mg/L of Iron
Daily Consumption of Hydrated Lime at Banning
60%
$201
$42
$360
Hydroxylation
Fe Removal
Calcite Formation

26. H2O2
Lime
Step 3: Develop alternative Treatment Strategy
to reduce Cost
Pilot Test 50% H2O2
– No pH adjustment

27. Mon-View H2O2
Step 4: Pilot test to gather performance
and cost data

28. Step 4: Pilot test to gather performance and
cost data
Banning H2O2

29. Step 5: Cost & Performance Analysis
between original and pilot systems
Monview Comparative Analysis
Reagent
Dose
(gal/day)
$/day
Effluent
pH
Effluent
T-Fe
(mg/L)
Original
System
20%
NaOH
122 $116 7.4 1.01
Pilot
System
35%
H2O2
14 $46 7.2 1.4
* NaOH = $.95/gal, H2O2 = $3.30/gal

30. Step 5: Cost & Performance Analysis
between original and pilot systems
Banning Comparative Analysis
Reagent
Dose
(gal/day)
$/day
Effluent
pH
Effluent
T-Fe
(mg/L)
Original
System
Ca(OH)2
3.77
ton/day
$603 8.25 1.0
Pilot
System
50% H2O2
& Ca(OH)2
25 gal/day
&
1.2 ton/day
$275 7.5 1.0
* Ca(OH)2 = $160/ton, H2O2 = $3.30/gal

31. Brandy Camp Trial 2012
Acidity Alkalinity Iron Iron Total Total TDS
Unfiltrd Filtrd Total Net Total Net Total Dissld Total Dissld Sulfate Susp.
at 105
C
Sample Flow pH Field Alk Iron
H2O2
Rate
Lab
"Hot"
Calculate
d Lab
Calcula
ted Fe Fe Mn Mn SO4
2- Solids
Date (gpm) (lab) (mg/L) (mg/L) (ml/min) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l)
5/1/2012 820.0 5.5 0.00 79.00 38.40 40.60 0.00 50.600 49.500 7.460 7.353 858.80 8.0 1408
5/8/2012 781.0 5.6 30.8 0.00 73.20 29.80 43.40 0.00 48.600 41.600 7.531 8.074 847.60 16.0 1366
5/9/2012 781.0 4.9 6.2 42.00 65.60 46.80 18.80 0.00 49.100 31.600 8.590 7.781 1703.1 44.0 1336
5/10/2012 781.0 3.8 0.0 42.00 73.00 73.00 0.00 0.00 53.540 17.200 8.059 7.690 820.00 88.0 1310
5/14/2012 781.0 3.8 0 80.00 80.00 80.00 0.00 0.00 53.480 15.620 8.097 8.003 842.70 8.0 1436
5/16/2012 781.0 3.9 0.0 80.00 81.00 81.00 0.00 0.00 52.000 16.300 7.465 7.588 828.20 82.0 1332
5/21/2012 781.0 3.7 0.0 1.6 80.00 71.80 71.80 0.00 0.00 51.500 13.000 8.091 7.614 761.70 86.0 1340
5/31/2012 692.0 3.6 0.0 1.1 75.00
105.4
0 105.40 0.00 0.00 51.700 14.800 7.729 7.882 809.80 94.0
6/7/2012 649.0 4.3 0.0 15.9 70.00 76.20 68.60 7.60 0.00 53.000 21.300 7.773 8.052 795.00 70.0 1342

32. $32,000/CLEAN OUT x TWICE YEAR

33. • Portion of Safety Film on Stability, Reactivity,
and Decomposition of H2O2
http://h2o2.evonik.com/product/h2o2/en/pages/h2o2-safety-training-video.aspx

34. • ALL OF THE PA DEP’S USE OR EVALUATION OF
HYDROGEN PEROXIDE ARE FOR ACTIVE
TREATMENT SYSTEMS WITH EXISTING, POWER
AND SOME TYPE OF SECURE FACILITIES.

35.  Ideal for Net Alkaline discharges with space limitations
 Low Capital Cost
 No additional TDS to final effluent
 Limits or eliminates calcite precipitation
 Stable supply and price structure
 Very low cost per gallon of water treated (typically $0.07
to $0.15 per thousand gals. Treated)
 Available in bulk delivery 35% and 50% are the most
common grades
 Low maintenance system (tank, pump and distribution line)
Pro’s (what’s great about H202)

36.  Stainless steel or plastic storage facilities and delivery
systems only (some very specific grades of Al will work)
 Containment and spill mitigation plan is absolutely
necessary.
 Personal Protective Equipment and Safety Training a must
 Not very effective for manganese removal
 Solids settling may require the use of additional and/or
different polymers than are used with traditional pH
adjusting chemicals
 VERY STRONG OXIDIZER must be respected at all times
Con’s (what’s not great about H202)

37. • Is Peroxide right for you?
Consider the site and staff availability. For most
watershed associations with strictly volunteer
labor and remote systems without power or safety
facilities, it is not a good idea.
If you need enhanced treatment, more control on
an effluent, or less sludge generation at an active
treatment plant, it may be a very useful component
to your treatment process.

38. • QUESTIONS AND ANSWERS