The document discusses the establishment and goals of the Clean Water Act to protect surface water quality in the US. It notes that while the Act aims to reduce pollutant discharges and restore water integrity, the treatment requirements for manganese have unintended consequences. Specifically, targeting manganese requires highly alkaline conditions that increase dissolved solids, osmotic pressure, and sludge volumes. It can also cause aluminum, which is toxic, to resolubilize. The document argues that manganese itself is not generally toxic at levels found in mine drainage and that alternative regulatory approaches are needed to avoid problems stemming from over-treatment.

1. Which Was Responsible for Establishment of
the CWA-”Clean Water Act”?

2. Clean Water Act
The Clean Water Act (CWA) is the cornerstone of surface water
quality protection in the United States. (The Act does not deal
directly with ground water nor with water quantity issues.) The
statute employs a variety of regulatory and non-regulatory tools to
sharply reduce direct pollutant discharges into waterways, finance
municipal wastewater treatment facilities, and manage polluted
runoff. These tools are employed to achieve the broader goal of
restoring and maintaining the chemical, physical, and biological
integrity of the nation's waters so that they can support "the
protection and propagation of fish, shellfish, and wildlife and
recreation in and on the water."

3. Total Concentration LimitsTotal Concentration Limits
VersusVersus
Dissolved Concentration LimitsDissolved Concentration Limits
First Major MistakeFirst Major Mistake
Which one of these is toxic to Aquatics?

4. Total Concentration Lab Prep.
After obtaining a water sample in the field and fixing it with nitric
acid, we send it to the lab for analysis. The first thing the lab does
is to digest the sample in preparation for analysis as described
below.
As might be imagined, this process
breaks the bonds and whatever metals
were complexed in the suspended solids
are now released to be measured as a
Total concentration.

5. Initial Limits assigned on basis Fe and Mn
found at 313 surveyed mine sites and using
Mn as a Surrogate to other Heavy Metals
 Discharges <6 pH
• Iron = 3.5-7 mg/l
• Manganese = 2-4 mg/l
• pH = 6-9
 Discharges >6 pH
• Iron = 3.5-7 mg/l
• pH = 6-9
Second Major Mistake!!!!!!!!!!!!

6. TMDL AND ANTI-DEG NPDES LIMITSTMDL AND ANTI-DEG NPDES LIMITS
 Between 1985 and 1995 WV was forced to implement TMDL’s and Anti-
degradation programs.
 These programs calculated limits depending if the stream did not meet its
designated use (TMDL’s) or if it did meet its designated use (Anti-degradion).
 Due to a lack of financial resources to properly categorize the streams, West
Virginia declared all streams in the state to be of drinking water quality which
had quality requirements of:
pH = 6-9
Iron = 1.5 mg/l
Manganese = 1.0 mg/l
Al = 0.75 mg/l
 Implementation of these programs essentially eliminated Technology Based
(BAT) effluent limits in favor of all calculated limits.

7. BAT Limits Vs. Calculated Limits
 BAT <6 pH
• Iron = 3.5-7 mg/l
• Manganese = 2-4 mg/l
• pH = 6-9
 BAT >6 pH
• Iron = 3.5-7 mg/l
• pH = 6-9
 Antidegradation
• Iron = 0.05
• Manganese = 0.04
• Aluminum = 0.06
• pH = 6-9

8. TREAT THIS WATER?????

9. MINE DRAINAGE FROM UNDERGROUNDMINE DRAINAGE FROM UNDERGROUND
MINE DRAINAGE may originate from three different sources underground.
The three sources are the roof, the coal seam, and the bottom.

10. MINE DRAINAGE FROM SURFACEMINE DRAINAGE FROM SURFACE
MINESMINES
MINE DRAINAGE surface sources include surface mine spoil, preparation plant
stockpiles, deep mine stockpiles, load-out storage areas, coal seam itself, pile of
pyrite tailings, etc…

11. Mine Drainage Comes in 2 Variety’s
Alkaline Drainage which may contain IronAlkaline Drainage which may contain Iron
and Manganese.and Manganese. “Potential Source being“Potential Source being
Siderite Solubilization”Siderite Solubilization”
Acidic Drainage which may contain Iron,Acidic Drainage which may contain Iron,
Manganese, Aluminum, and PotentiallyManganese, Aluminum, and Potentially
other heavy Metals.other heavy Metals. “Potential Source“Potential Source
being Pyrite Oxidation”being Pyrite Oxidation”

12. PRIMARY CHEMICALS FOR TREATMENT
 Sodium Hydroxide
 NaOH + H2O = Na + OH +H2O
 Calcium Oxide
 CaO + H2O = Ca(OH)2 = Ca + (OH)2
 Ammonia
 NH3 + H2O = NH4 + OH
 OH IS THE SYMBOL FOR ALKALINITY OR HYDROXYL ION
 WHAT DO YOU GET WHEN ADDING ALKALINITY TO ACIDITY?

13. ALKALINITY + ACIDITY
OH + H = H2O

14. PH FOR METAL
REMOVAL
 ALUMINUM--------------4.21-7.00 PH
 FERRIC IRON-----------3.50-5.00 PH
 FERROUS IRON--------8.40-9.30 PH
 MANGANESE----------9.00-10.50 PH
 MAGNESIUM---------10.20-11.00 PH

15. Caustic Soda (NaOH)Caustic Soda (NaOH)
DispensingDispensing
ContainersContainers
Sodium HydroxideSodium Hydroxide

16. SOLID CAUSTICSOLID CAUSTIC
Solid caustic is anhydrous which results in a thermal reaction when water is added.

17. PEBBLE LIME - CALCIUMPEBBLE LIME - CALCIUM
OXIDEOXIDE
Pebble quicklime is generally fed to the AMD stream with a water-wheel.

18. Hydrate Lime (Ca(OH)2)

19. AMMONIA INJECTIONAMMONIA INJECTION
Ammonia has been injected into ponds from single source injectors.
The optimum method of ammonia injection is on a continuous basis to moving water.

20. OXIDIZERS TO REMOVEOXIDIZERS TO REMOVE
MNMN
POTASSIUM PERMANGANATE HYDROGEN PEROXIDE SODIUM HYPOCHLORITE

21. ““OTHER” TREATMENTOTHER” TREATMENT
MINE DRAINAGE treatment can get “exciting”

22. ZEOLITE
Parameter Raw Water After Zeolite
pH 3.31 5.71
Dissolved Fe 2.48 0.21
Dissolved Mn 32.23 8.27
Dissolved Al 48.82 0.11
Sample 1
Parameter Raw Water After Zeolite
pH 2.97 5.32
Dissolved Fe 9.23 0.22
Dissolved Mn 53.13 14.83
Dissolved Al 52.24 0.46
Sample 2

23. TREATMENT FOR MN PRODUCES SLUDGETREATMENT FOR MN PRODUCES SLUDGE

24. WHAT TO DO WITH THE SLUDGE SLUDGE?WHAT TO DO WITH THE SLUDGE SLUDGE?

25. ““PASSIVE” TREATMENTPASSIVE” TREATMENT
Wetlands-Vertical Flow Ponds-Bioremediation
Mn Limestone beds-Hybrids

26. VERTICAL FLOW POND USING SLAGVERTICAL FLOW POND USING SLAG

27. ““MANGANESE ART”MANGANESE ART”
Over Treatment for Manganese with Magnesium precipitation

29. RAISING PH PRECIPITATES METALS & GENERALLYRAISING PH PRECIPITATES METALS & GENERALLY
INCREASESINCREASES
DISSOLVED SOLIDS/CONDUCTIVITY/DISSOLVED SOLIDS/CONDUCTIVITY/ OSMOTIC PRESSUREOSMOTIC PRESSURE
Sample ID pH Dissolved Iron Dissolved Manganese Dissolved Aluminum
Raw Water 2.94 8.45 4.05 5.36
Increment 1 5.00 <0.01 4.43 1.06
Increment 2 6.00 <0.01 4.80 0.08
Increment 3 7.03 <0.01 4.28 0.26
Increment 4 8.06 <0.01 4.03 0.24
Increment 5 9.09 <0.01 3.22 0.16
Increment 6 10.00 <0.01 2.07 0.15
Increment 7 10.26 <0.01 1.03 0.14
Sample ID pH Dissolved Fe Dissolved Mn Dissolved Al Dissolved Mg Dissolved Ca
Raw Water 2.94 8.45 4.05 5.36 68.60 266.20
Increment 7 10.26 <0.01 1.03 0.14 23.80 659.60
As with nearly all AMD chemical treatment systems, you always end up with more cations than when
you started. From the chart, we find that we removed 8.45 mg/l of iron, 3 mg/l of manganese, 5.22 mg/l
of aluminum, and because we treated to a high pH for manganese removal—44.80 mg/l of magnesium.
This means that we removed 61.47 mg/l of metals through treatment. However, the lime used to raise
the pH dissolved an additional—659.60-266.20=393.40 mg/l of calcium. When accounting for what was
removed, we have 393.40-61.47=331.93 mg/l more dissolved cations than when we started which
increases Osmotic Pressure and obviously Conductivity. Osmotic Pressure/Conductivity trumps 4 mg/l
of manganese, especially when there are no toxicity related problems with manganese.

30. ADDITIONALADDITIONAL PROBLEMSPROBLEMS DUE TO TREATMENT FORDUE TO TREATMENT FOR
MANGANESEMANGANESE
ARE RELATED TO HIGH PH DISCHARGES AND INCREASEDARE RELATED TO HIGH PH DISCHARGES AND INCREASED
SLUDGE VOLUMESSLUDGE VOLUMES
Time pH
8:00 AM 10.26
8:30 AM 10.10
9:00 AM 10.03
9:30 AM 9.97
10:00 AM 9.87
10:30 AM 9.79
11:00 AM 9.73
11:30 AM 9.64
12:00 AM 9.58
12:30 PM 9.51
1:00 PM 9.42
1:30 PM 9.38
2:00 PM 9.32
2:30 PM 9.21
3:00 PM 9.19
3:30 PM 9.15
4:00 PM 9.11
4:30 PM 9.07
5:00 PM 9.02
5:30 PM 9.00
Time required for pH
To Buffer to a 9 pH
Treatment for Fe & Al
Treatment for Fe & Al & Mn = Twice the Sludge Volume

31. ONE FINAL PROBLEMONE FINAL PROBLEM DUE TO TREATMENT FORDUE TO TREATMENT FOR
MANGANESEMANGANESE
“ALUMINUM RESOLUBILIZATION”“ALUMINUM RESOLUBILIZATION”

32. IN SUMMARY:
PRO’S AND CON’S OF MANGANESE REMOVAL
PRO’S
1-Made someone who doesn’t
understand water chemistry feel
like they really accomplished
something good for man-kind.
CON’S
1-Extremely High pH required for removal.
2-Treatment increases Osmotic Pressure.
3-Sludge volumes are 2-3 times more.
4-Aluminum that is toxic, is resolubilized.
5-Cost to remove Mn is 1.5-3 times higher.
6-Ultimately, the States will assume treatment.
7-Joe Tax Payer will pay for with higher taxes.
Regulatory Tools to Avoid Toxic Effects Associated With Treatment for Manganese
1-Use of Alkaline Mine Drainage Limits
2-Use of Post Mining Limits
3-Institute something like WV 5 Mile Rule to make 1 and 2 Possible
4-Re-Evaluate Stream Designated Use Category

33. CONCLUSION
Manganese has been Misunderstood, Mis-Regulated, and Mistaken
for a Problem, for which it is not. If you wish to fulfill the goals of
the Clean Water Act (“achieve the broader goal of restoring and
maintaining the chemical, physical, and biological integrity of the
nation's waters”) , then you will find a way to correct a pollution
problem that the CWA created 40 years ago and is still ongoing today.
You will do everything you can to reduce the increased dissolved
solids problem, reduce the increased Osmotic pressure problems,
eliminate wasteful spending on inflated treatment costs, reduce sludge
volumes and the associated disposal problems, reduce unnecessarily
high treatment pH values, and eliminate aluminum resolubilization, all
caused by the indiscriminant treatment for “a problem that does not
exist”.