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

Clean Water ActThe 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."

Total Concentration LimitsTotal Concentration LimitsVersusVersus

Dissolved Concentration LimitsDissolved Concentration LimitsFirst Major MistakeFirst Major Mistake

Which one of these is toxic to Aquatics?

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.

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!!!!!!!!!!!!

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 = 6-9Iron = 1.5 mg/l

Manganese = 1.0 mg/lAl = 0.75 mg/l

Implementation of these programs essentially eliminated Technology Based (BAT) effluent limits in favor of all calculated limits.

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

TREAT THIS WATER?????

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.

MINE DRAINAGE FROM SURFACE MINESMINE DRAINAGE FROM SURFACE MINES

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…

Mine Drainage Comes in 2 Variety’s

Alkaline Drainage which may contain Iron Alkaline 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 Potentially Manganese, Aluminum, and Potentially other heavy Metals. other heavy Metals. “Potential Source “Potential Source being Pyrite Oxidation”being Pyrite Oxidation”

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?

ALKALINITY + ACIDITY

OH + H = H2O

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

Caustic Soda (NaOH)Caustic Soda (NaOH)

Dispensing Dispensing ContainersContainers

Sodium HydroxideSodium Hydroxide

SOLID CAUSTICSOLID CAUSTICSolid caustic is anhydrous which results in a thermal reaction when water is added.

PEBBLE LIME - CALCIUM OXIDEPEBBLE LIME - CALCIUM OXIDEPebble quicklime is generally fed to the AMD stream with a water-wheel.

Hydrate Lime (Ca(OH)2)

AMMONIA INJECTIONAMMONIA INJECTIONAmmonia has been injected into ponds from single source injectors.

The optimum method of ammonia injection is on a continuous basis to moving water.

OXIDIZERS TO REMOVE MNOXIDIZERS TO REMOVE MN

POTASSIUM PERMANGANATE HYDROGEN PEROXIDE SODIUM HYPOCHLORITE

““OTHER” TREATMENTOTHER” TREATMENTMINE DRAINAGE treatment can get “exciting”

ZEOLITE

Parameter Raw Water After ZeolitepH 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

TREATMENT FOR MN PRODUCES SLUDGETREATMENT FOR MN PRODUCES SLUDGE

WHAT TO DO WITH THE SLUDGE SLUDGE?WHAT TO DO WITH THE SLUDGE SLUDGE?

““PASSIVE” TREATMENTPASSIVE” TREATMENTWetlands-Vertical Flow Ponds-Bioremediation

Mn Limestone beds-Hybrids

VERTICAL FLOW POND USING SLAGVERTICAL FLOW POND USING SLAG

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

RAISING PH PRECIPITATES METALS & GENERALLY INCREASESRAISING PH PRECIPITATES METALS & GENERALLY INCREASESDISSOLVED 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 5.36Increment 1 5.00 <0.01 4.43 1.06Increment 2 6.00 <0.01 4.80 0.08Increment 3 7.03 <0.01 4.28 0.26Increment 4 8.06 <0.01 4.03 0.24Increment 5 9.09 <0.01 3.22 0.16Increment 6 10.00 <0.01 2.07 0.15Increment 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 68.60 266.20Increment 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.

ADDITIONALADDITIONAL PROBLEMSPROBLEMS DUE TO TREATMENT FOR MANGANESE DUE TO TREATMENT FOR MANGANESEARE RELATED TO HIGH PH DISCHARGES AND INCREASED ARE RELATED TO HIGH PH DISCHARGES AND INCREASED

SLUDGE VOLUMESSLUDGE VOLUMES

Time pH   

8:00 AM 10.268:30 AM 10.109:00 AM 10.039:30 AM 9.97

10:00 AM 9.8710:30 AM 9.7911:00 AM 9.7311:30 AM 9.6412:00 AM 9.5812:30 PM 9.511:00 PM 9.421:30 PM 9.382:00 PM 9.322:30 PM 9.213:00 PM 9.193:30 PM 9.154:00 PM 9.114:30 PM 9.075:00 PM 9.025:30 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

ONE FINAL PROBLEM ONE FINAL PROBLEM DUE TO TREATMENT FOR MANGANESEDUE TO TREATMENT FOR MANGANESE“ALUMINUM RESOLUBILIZATION”“ALUMINUM RESOLUBILIZATION”

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’S1-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 Manganese1-Use of Alkaline Mine Drainage Limits

2-Use of Post Mining Limits3-Institute something like WV 5 Mile Rule to make 1 and 2 Possible

4-Re-Evaluate Stream Designated Use Category

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”.