Understanding the Science and Synergy in Chemistries & Processes

LeRoy Palmer Todd Eden

“The First Step to Solving a Problem

is Identifying the True Problem”

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Why? Can this Industry Trend be Changed?

The Gradual Death of a Well

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Well Performance Measurement

Yield in GPM / Drawdown in Feet (ftdd)

Yield = 200 GPM / Drawdown = 50 ftdd

200 GPM / 50 ft.

Specific Capacity = 4 GPM/ftdd

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It’s just water . . . right?

Evidently Not . . . T

And Every Well is

Unique!

• Age • Materials of

Construction • Historical Maintenance • Frequency and Duration

of use/non-use • Geography • Hydrogeology • Water Quality

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Is it just Iron and Water Rust?

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Is it just Dirt and Scale?

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There are Vast Differences . . .

Well Scale

Well Scale Well Scale

Iron Bacteria

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These ALL have the SAME Problems

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Minerals + Metals + Microbes

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Minerals, Scale, Salts

Calcite Well Scale Caliche & Brine Scale Microbial Induced

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Metals – Iron, Corrosion

Iron Metal and Rust

Microbial Induced Tubercles of Iron with trace Minerals

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Microbes

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Microbes Algae Bacteria Fungi Yeast Mold Mildew Slime, Filamentous Spore Forming Aerobic (with oxygen) Anaerobic (without oxygen) Exponential Reproduction

The True Problem – The 3 M’s

Minerals

Calcium Magnesium Silica Potassium Phosphate Sulfate TDS

Metals Iron Copper Manganese Corrosion Products Also TDS

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Bacteria & Coliforms

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Iron Bacteria (Iron, Sulfate, Manganese Utilizing Species)

Sphaerotilus Leptohrix Galionella

Ferruginea

Can help hide/protect

pathogen growth

Coliforms / E.coli

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Iron Bacteria Iron Sludge Iron Tubercles

"It can get away with surviving using stuff besides oxygen, like iron and sulfate"

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Non-pathogenic Common Soil Bacteria

Slime Forming Pseudomonas Aerobacter Flavobacter Acinetobacter Plugging / stalks (corrosive enzymes) Gallionella Crenothrix Lepothrix Siderocapsa Corrosion & Odors (hydrogen sulfide gas - lethal) Sulfate Reducing Bacteria Iron Bacteria Families

2,000 Tests 88% the problem Found in wells and systems 8% the problem

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Tubercles, Nodules, MIC, SRB’s

Bacteriological Acid Localized Corrosion 22 mils per year on mild steel. Crevice failure appears rapidly.

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Microbial Induced Corrosion

22 mils per year on Iron Bottom 2 Images are Stainless Steel

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Descale? Disinfect? Biodisperse? Biocide? Mineral? Metal? Microbe?

Decisions . . .

Volume? Energy? Time?

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Why do Organisms . . . Non-toxic anti-sticking coatings prevent attachment of microorganisms thus negating the use of biocides. These coatings are usually based on organic polymers, which allow researchers to add additional functions too, such as antimicrobial activity. There are two classes of non-toxic anti-fouling coatings. The most common class relies on low friction and low surface energies. This results in hydrophobic surfaces. These coatings create a smooth surface which can prevent attachment of larger microorganisms. For example, fluoropolymers and silicone coatings are commonly used. These coatings are ecologically inert but have problems with mechanical strength and long term stability. Specifically, after days, biofilms (slime) can coat the surfaces which buries the chemical activity and allows microorganisms to

attach. (2)

Attach? To absorb nutrients.

Encrust? Protection.

Excrete Polysaccharides?

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Polysaccharides

• Pathogenic bacteria commonly produce a thick, mucous-like, layer of polysaccharide.

• … nearly two hundred different polysaccharides are produced by E. coli alone.

• Polysaccharides help adhere and protect.

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Colony Forming Units Bacteria

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Why have we been

Brushing & Bailing

without a Biocide?

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The Disparity Between

Chlorine Biodispersants

Biocides

For Microbial Removal, Reduction, Suppression

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Chlorine Chlorine / Disinfectants destroy microorganisms by attacking their cell wall.

Mostly effective on soluble organisms and minor biofilms.

Overuse causes barriers to effectiveness – do not exceed 200 ppm at any given

treatment – exercise pH adjustment with multiple treatments between flushing

and supplements

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Biodispersants

“Biodispersants improve the separation of bio-matter and are designed to prevent

their settling or clumping.”

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Biocide

“Biocides are a chemical substance or microbe which can deter, render harmless, or exert a controlling effect on any harmful

organism by chemical or biological means. Biocides are intended to destroy microbial life, including penetrating the cellular walls and

spores destroying the organisms DNA.”

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Chlorination Problems

1. Super chlorination levels of 1000, 2000 and 5000 mg/L may not be effective

2. 500 mg/L failed about 50% of the time

3. High concentrations are very oxidative 4. Higher levels can be greater than pH 10

and ineffective at that level 5. High pH promotes mineral precipitation

6. Strong oxidation changes the polysaccharide which hardens the biofilm covering

The most effective disinfection levels were the 50 mg/L and the 200 mg/L of Chlorine

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Chlorination Insights & Observations

1. Disinfect according to current AWWA & EPA protocols. 2. If you have a biological problem, increase the frequency of

disinfection, not the quantity of chlorine per treatment. 3. Adjust your water pH to optimize your disinfection. 4. Chlorine is not effective in stagnant water conditions. 5. Chlorine is not effective against spore formed organisms ,

tuberculation or nodules. 6. Chlorine is corrosive, oxidized iron is microbial food. 7. If you are continually battling microbial issues requiring

disinfection, you probably have a microbial infestation and should consider cleaning the well and using a biocide.

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Biocide Insight (HP = Hydrogen Peroxide)

1. If you think chlorine or acid is corrosive – wait till you see HP. 2. DO NOT USE HP without a qualifying inhibitor – it will destroy

rubber seals and noble metals. 3. HP can be catalyzed 100 to 1,000 times more effective. 4. HP penetrates and destroys the DNA of spore forming

organisms. 5. Overuse of HP does not toughen bio-film or polysaccharide. 6. In case of spill – add water to achieve a 3% dilution. 7. HP diluted must be used the same day. 8. HP completely degrades to oxygen and water within 7-21 days. 9. Interesting that a 50% solution will not freeze until -50 Deg. C.

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Water Well Cleaning Goals

Minerals Metals Microbes Brush and Bail Acid Acid Biocide Brush, Bail, Swab, Bail Acid Acid Biocide --------------Soak Time, Energy------------ Passivate/Neutralize Downhole – Sodium Bicarbonate (Soda Water) Above Ground – Sodium Bicarbonate or Soda Ash

Develop & Disinfect Chlorine and pH Adjustment Controlled energy products with the proper acid and biocide is typically endorsed with qualifying circumstances.

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Chemistry, Processes and Procedures

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There are Vast Differences in Descalers

• Scale Dissolving Volume • Scale Dissolving Rate • Iron Sludge Dissolving Rate • Iron Bacteria Dissolution • Spore and Nodule Dissolution • Corrosion Inhibitor Capacity and Longevity • Biocide Capacity and Longevity • Mineral and Metals Solubility Limitations • Chemical Synergy & Compatibility Against Organisms • Discharge Effluent, Flushing Volume • Dissolved, dispersed and suspended solids • Foaming • Conditioning and Developing the well into service

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Scale Dissolving Research

* Solubility Threshold Limitations

Rank Product (25 grams total) Scale Dissolved,

grams

1 Sulfamic Acid 13.0

2 Sulfamic Acid with catalyst 11.3

3 HCl 34% with catalyst 9.8

4 HCl 34% 9.5

5 Product 310 9.0

6 Product 21 9.0

7 Phosphoric Acid 75% 7.6

8 Phosphoric Acid 75% with catalyst and Peroxide 7.0

9 Citric Acid 6.9

10 Citric Acid with catalyst and Peroxide 6.7

11 Product M&A 6.6

12 Product LD 4.9

13 Product OS 4.9

14 MI SWACO Ringfree 0.0

15 Bicrabus 0.0

16 Oxalic Acid (0.9)

17 Oxalic Acid with catalyst and Peroxide (0.9) T

Solubility Thresholds

Substance Formula 20 °C - 68° F

Solubility

Calcium acetate Ca(C2H3O2)2.2H2O 34.7000

Soluble Magnesium sulfate MgSO4 35.1000

Calcium bicarbonate Ca(HCO3)2 16.6000

Monocalcium phosphate Ca(H2PO4)2 1.8000

Insoluble

Magnesium carbonate MgCO3 0.0300

Calcium sulfate CaSO4.2H2O 0.2500

Dicalcium phosphate CaHPO4 0.0043

Calcium phosphate Ca3(PO4)2 0.0020

Magnesium phosphate Mg3(PO4)2 0.0002

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HCl at pH 3.0 carries 12,000 ppm TDS. With dispersion chemistry HCl at pH 3.0 can carry 120,000 ppm TDS – x10 As acid is spent, pH rises. HCl at pH 4.0 only carries 2,400 ppm TDS With dispersion chemistry HCl at pH 7.0 carries a whopping 108,000 ppm TDS - x45

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Scale Dissolving Rates

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Corrosion Inhibition Characteristics

pH is NOT the indicator

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2014 Game Changing Research

Brushing, Bailing, Cleaning - Do we really want to spread or embed colony forming units throughout the well when brushing, bursting or pressure washing without having an effective biocide in place?

How are screened intervals cleaned without embedding biomatter and debris into the gravel pack and strata?

How much scale does one chemical dissolve over the other, and over what time?

Maintain pH below 3. Right or Wrong?

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Maintain pH below 3. Right or Wrong?

Parameter HCl 10% HCl 9% WK 1%

Variance

pH 2.7 1.5 N/A

Calcium 7,950 9,140 13%

Magnesium 85 90 6%

Calcium Hardness 19,800 22,800 13%

Magnesium Hardness 351 371 5%

Total Hardness 20,200 23,200 13%

TDS 33,700 34,600 3%

Results after complete saturation with well scale

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The Case for Downhole “Passivation”

CHLORIDES + Entrained Acid + Iron Casing/Soluble Iron = CORROSION = Nutrients for Iron Bacteria Entrained acid and chlorides in gravel pack, behind casing, absorbed into the granular structure of metals. NEW - Passivate & Neutralize with Sodium Bicarbonate (soda water). Traditional - Neutralize above ground

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Notables . . . Synergy in chemistry, process and procedures For the treatment of Minerals, Metals and Microbes Q: Should cleaners and biocides be used together? A: If they are labeled compatible, yes. 1. Scale and corrosion products are food for organisms. Stirring up organisms propagates microbes throughout the environment . Microbes are colony forming units. You want as few colony forming units as possible. 2. Also, bio-films are resistant to acid just like scale is not easily dissolved by biocides.

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Hydrogen Sulfide Gas

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Take-A-Ways

1. The synergy between chemistry, process and procedures define optimum results.

2. Professional Assessments can be priceless.

3. Activity downhole without effective microbiological control can cause the premature death of water wells - Brush and Bail with “Corrosion Inhibited Biocide”

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5. Biocides are effective at penetrating and breaking down bio-film and polysaccharides – acids are not.

6. Energy products embed bio-matter . Use protective measures against bio-film and polysaccharides.

7. Downhole passivation is essential 8. Proper application of chlorine is essential 9. Chlorine, disinfectants and biodispersants are

only effective on surface and soluble organisms.

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Effective Removal of Bio-films

Acid Disinfectant Biodispersant Biocide

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Assists

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HCl HCl + H2O2

HCl + H2O2+++

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Industry Advancements

• Pump in place (insitu) Well Maintenance • Pump in place (insitu) Well Rehabilitation • Well Restoration • Corrosion Inhibited Biocides • Water Well Layup Chemistry • Downhole passivation / Neutralization • Differences in chemistry, processes and procedures • Synergy between chemistry, processes and procedures • History of the well is critical to the best diagnoses • pH is not a valid indicator of acid descaling or corrosivity • Chemical solubility thresholds are important

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Questions . . .

Thank you

L&T