Water Quality and Chemistry

WaterQuality and Chemistry

LFKS 18 May 2011

Ian Millichip

Water Quality and Chemistry

Aims
1. 2. 3. 4. 5. 6.

Emphasise the wonders of water and some science of water. De-mystify some parts of water chemistry and show patterns BUT.some bits will confuse even more! Explain the meaning and Relationship of common water quality parameters Discuss the measurement and relation of water parameters to fish health Set a platform for future study
Ian Millichip

Water Quality and Chemistry

Overview
Water. The Magic Chemical Directions Measurements and Meaning pH/Acidity/Basicity/Alkalinity pH Buffers Hardness Redox Methylene blue Nitrogen Cycle and filtration Water Treatment/Chlorine/chloramine Magnesium/Calcium complex convolution

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Water Quality and Chemistry

Some Food for Thought (first)

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Water Quality and Chemistry

If the pH is acidic does all ammonia exist as ammonium? NO * Can pH be low and Alkalinity be high? YES Can you have Soft Alkaline water? YES If you measure pH, can you know how much acid is in the aquarium? NO *
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Water Quality and Chemistry

Water Is
Oxidane An Anomoly

Water Liquid at Room Temp Hydrogen Sulphide toxic gas Selenium Hydride toxic flammable gas

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Water Quality and Chemistry

Water Is

Magical Great Solvent (but not for water) Specific heat capacity (High) Heat of Vaporization ~ Humidity Air Miscibility and condensation / From Ice to Gas Density of Water vs Ice (4 C) Low Compressibility Cohesion and adhesion
Surface tension (cohesive strength) Capillary action (adhesive strength)

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Water Quality and Chemistry

Water Is

Life
Cradle of Life Vital Biochemical

Water to Oxygen Oxygen to Water Hydrolysis/Catalyst Substrate Destroys Cells

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Water Quality and Chemistry

Chemistry is about Changes

But Change cannot be any old Change.
Chemistry in 3 Human Scenarios
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Water Quality and Chemistry

Change

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Water Quality and Chemistry

Change
HIGH ENERGY

In Short..
Chemistry is A downhill slippery and messy slope with

Getting to Equilibrium and

Having Minimum Energy AND

Giving out the Most Useable Energy

LOW ENERGY

With the Maximum Entropy (=mess or chaos)

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Water Quality and Chemistry

Change Rule is: 1/3 downstairs

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Water Quality and Chemistry

Getting Down to Business

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Water Quality and Chemistry

Starting With

Getting some water

Water/Metals/Chlorine/Chloramine/Salts/ Water/Metals/Chlorine/Chloramine/Salts/ Acids/Bases/Carbonates/other molecules
Water Conditioner

R.O. Unit

?? What is in it ??

Fish Tank

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Water Quality and Chemistry

What is in the Bucket?

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Water Quality and Chemistry

Conditioners

Dechlorination
Sodium thiosulphate (produces ammonia from Chloramines)

Sodium hydrosulphite (eg Seachem Prime as a complex) Sodium hydroxymethylsulfinate (eg AquaSafe) Sodium hydroxymethanesulfonate (eg Amquel)

Heavy Metal Removal

In some, but not all. Organic or Synthetic Chelating agents.

Slime Coat Protection

aloe vera and other herbals carboxymethylcellulose Polyvinylpyrrolidone

Other Additives
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Water Quality and Chemistry

RO System & Chloramines

Ammonia + Chlorine + HCl
~ pH

Chloramines
To RO Unit

Lower pH > Ammonia + ^pH Ammonium And reduce Membrane Swelling

Ammonia (UIA)

Activated Carbon
(Low Peroxide No.)

RO Membrane
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pH > 7.5

Water Quality and Chemistry

Acids/Bases et al

pH one of the measures of acidity/basicity

- log10 {Hydrogen ion} ( approx = - log10 [Hydrogen ion] ) Affected by Temperature / Concentration / ionic strength

Acid
Donate a hydrogen ion to solution (classical understanding); OR Accepts an electron pair (eg Aluminium Chloride)

Base
Accepts a hyrdrogen ion; OR Donates an electron pair

pH Buffer
Resists changes of pH on addition of a small amount of acid or base Often mix of a weak acid or weak base and the salt of a weak acid or weak base

Alkalinity
Type of buffering. MEASURE..solutions ability to neutalise an acid. Linked in Aquaria to Carbonate buffering (and hardness)

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Water Quality and Chemistry

Hardness
Classically.Hard to form a lather Temporary Hardness

Easily removed by boiling heating decomposes soluble Bi-carbonates (Hydrogen Carbonates) to insoluble Carbonates

Permanent Hardness

Soluble calcium and magnesium salts

eg Calcium and Magnesium chlorides and sulphates

Removed

by

Distillation/De-ionisation/Ion Exchange/RO/Chemical Reaction

Measuring.. KH vs GH.depends exactly on what is being measured by a Test Kit.

GH and KH are NOT chemically or mathematically related.

Different units used in different test (DH. ppm, Clarkes)

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Water Quality and Chemistry

Hardness

Contributes or Affects
General stability pH pH Buffering Alkalinity RedOx and RedOx Balance Ionic balance/conductivity/TDS Diffusion/Osmosis Nutrient Uptake Supply of vital minerals: calcium & magnesium

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Water Quality and Chemistry

Conductivity (and TDS ?)

Carnegiella marthae (hatchetfish) 20-50 S/cm Chocolate Gourami Pterophyllum altum Symphysodon discus Three-lined pencilfish Cardinal tetra Clown Loach Dwarf Gourami Ram Cichlid Symphysodon aequifasciatus Corydoras julii Pearl Gourami Tiger Barb Pterophyllum scalare Apistogramma sp Glass catfish, Ghostfish Neon Tetra Most Corydoras Kribensis Cichlid Red piranha Rosy barb Siamese fighting fish Three-spot gourami Zebra Danio

200-500 S/cm

50-100 S/cm

> 500 S/cm

Malawi Cichlids Indian glass fish Firemouth & Convict Cichlid (and some other Cichlosoma type cichlids) Platy & Swordtail Most Rainbow Fish White cloud mountain minnow American Flag Fish (Jordanella floridae) Scatophagus argus Celebes Rainbow Fish Molly & Guppy Goldfish Tanganyikan Cichlid

100-200 S/cm

Conductivity Affected by..

Changing pH (up/down)..messing Changing Hardness Balancing Alkalinity, Mg and Ca etc Topping up water/ lack of water changes

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Water Quality and Chemistry

RedOx
RedOx = Reduction and Oxidation RedOx Balance is vitally important. Complex RedOx Potential (ORP)

Potential

to Donate Electrons (Reducing Environment) Potential to Accept Electrons (Oxidising Environment) Is just a measure (and askwhat is measured?)

+300 (Ox) to -100(Red) mV (marine); +125 to -200 mV (freshwater)

Reducing Environment is ideal for fish health Oxidising Environment is good for sterilising RedOx balance can get run-down with time.

Regular Partial Water changes; good aeration Having a good buffer Monitoring and maintain pH, Alkalinity, Hardness help.

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Water Quality and Chemistry

RedOx
Vital Consideration
The basis of life existing pivots around RedOx Potentials General Health and Water Quality In Aquaria(for examples).

Exchange across Gills Interaction at mucous layer Dropsy/Kidney Function/ Exploitation of substrate buffering Old-Water syndrome Biological Filtration Decay upsets RedOx Balance Treatment of Disease Treatment of certain poisonings

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Water Quality and Chemistry

Methylene Blue
RedOx Agent

Key Treatment in Aquaria

Photosensitiser

Stain for microscopy and clinical diagnosis Redox Indicator ** Methaemoglobinaemia / Cyanide Poisoning / Carbon Monoxide Poisoning **

** = my academic area of study

Hepatitis C/ Kaposi's sarcoma/ inactivates Staphylococcus aureus Anti-Malarial Induces Cancer Cell Apoptosis ** Protects against Mustard Alkylating Agent Neurotoxicity ** Mono Amine Oxidase Inhibitorused to make antipsychotic drugs **

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Water Quality and Chemistry

Test Indicators
A pH Indicator (Thymol Blue) Nitrte/Nitrate Test

General Hardness Indicator

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Water Quality and Chemistry

Test Kits (Hints)

Take

Note of Best Before Date; Store as directed Keep ALL documentation Use a syringe to measure water sample. Do not cross-use (cross-contaminate) test phials

View test-results in good light

Be aware that test kits are not 100% accurate, and are 100% specific. Take special note if aquarium water is tinted If using drop-by-drop count, let drops simply drop

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Water Quality and Chemistry

Test Kits (Hints)

Thoroughly clean all phials immediately after use in RO/DI water; and dry phials Monthly, soak phials in distilled vinegar and rinse in RO/DI water; dry phials.

For probe-based equipment Make sure calibration fluids are proper standards Rinse in old calibration fluids before calibrating. Clean using distilled vinegar and store in RO/DI water Have water stirred whilst testing Treat as a Delicate Instrument
Precision versus Accuracy?
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Water Quality and Chemistry

Which Are Acids and Bases?

A lu m in iu m c h lo rid e A m m o n ia (N H 3 ) + A m m o n iu m io n [N H 4 ] B e n ze n e 2+ C a lc iu m Io n (C a ) C h lo rid e (C l ) C y a n id e (C N ) F e rric (Iro n III) c h lo rid e (F e C l 3 ), 3+ 2+ F e rric Io n (F e ); C u p ric Io n (C u ); F e rro u s Io n 2+ 2+ (F e ); L e a d II io n (P b ); + S ilv e r io n (A g ) H y d rid e Io n (H ) H y d ro g e n (H 2 ) + H y d ro g e n Io n o r P ro to n (H ) H y d ro x id e io n (O H ) M a g n e s iu m Io n (M g ) M e rc u ry (H g ); Iro n m e ta l (F e ) M e th a n e (C H 3 ) N itrite io n [N O 2 ] + O x o n iu m io n [O H 3 ] + S o d iu m io n (N a ) W a te r (H 2 O )
2+ -

A C ID B ASE A C ID B ASE A C ID B ASE B ASE A C ID A C ID

L o b e -L U M O L e w is a c id s L o b e -H O M O L e w is b a s e s O n iu m Io n L e w is a c id s H O M O L e w is b a s e s s -L U M O L e w is a c id s L o b e -H O M O L e w is b a s e s L o b e -H O M O L e w is b a s e s L o b e -L U M O L e w is a c id s H e a v y M e ta l L e w is a c id s

B ASE B ASE A C ID B ASE A C ID A C ID B ASE B ASE A C ID A C ID B ASE

s -H O M O L e w is b a s e s s -H O M O L e w is b a s e s P ro to n L e w is a c id L o b e -H O M O L e w is b a s e s s -L U M O L e w is a c id s H e a v y M e ta l L e w is a c id s L o b e -H O M O L e w is b a s e s L o b e -H O M O L e w is b a s e s O n iu m Io n L e w is a c id s s -L U M O L e w is a c id s L o b e -H O M O L e w is b a s e s

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Water Quality and Chemistry

Acids in Water

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Water Quality and Chemistry

pH (Strong Acid)
Hyrogen Chloride (HCl) In water = Hydrochloric Acid
(1 mole HCl = 36.5g)
Grams HCl 3700 1850 370 37 3.7 ~ pH 1.00 1.30 2.00 3.00 4.00

HCl + Pure Water

0.37
0.037 0.0037 0.00037 0.000037

5.00
5.96 6.70 6.96 7.00

1000 litres

0.0000037
0.00000037 0
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7.00
7.00 7.00

Water Quality and Chemistry

pH (Weak Acid)
Acetic Acid (HAc)
(1 mole HAc= 60g) pKa = 4.75
Grams HAc 6000 3000 ~ pH 2.88 3.03

600
60

3.38
3.88

4.38 4.88
5.37 5.85

HAc + Pure Water

0.6
0.06 0.006

0.0006
0.00006

6.29
6.63 6.85 6.95 7.00

1000 litres

0.000006 0.0000006 0
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Water Quality and Chemistry

pH (Weak Acid as Buffer)

HA( aq ) ( Acid ) H (aq ) conj ' Acid A(aq ) conj ' Base

{H }{ A } Ka {HA}

pK a Log10 ( K a )

pH Log10 ( {HA}K a )

pKa1 pKa2 pKa3

2.1 7.2 12.4

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Water Quality and Chemistry

Nitrogenous Compounds

Amino Acids from Proteins >

Building Proteins/ Converted to Fat or Sugars or other biochemicals Compromise energy and water needs in disposal.

Surplus amino acids need to be excreteddepends upon the bodys water demands and supply.

Reptiles > urates/uric acid with very little water Marine Fish > dimethyl amine or as urea in blood In humans > urea dissolved in plenty of water Freshwater fish > direct movement of ammonia out of gills (mainly by passive diffusion) Diffusion of Ammonia out of fish depends on ammonia in outside water and pH.

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Water Quality and Chemistry

Nitrogenous Compounds
In the Aquarium
Amino Acids / Waste / Dead fish / uneaten food
Ammonification [RAPID]

Ammonia (NH3)
0.06 mg/L

Nitrous Acid/Nitrites (NO2)

0.5 mg/L

Nitrosofication (Nitroso-bacteria + Oxygen)

Nitrification (Nitro-bacteria + Oxygen)

Nitric Acid/Nitrates (NO3)

90.0 mg/L
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Water Quality and Chemistry

Ammonia

Total Ammonia = Ammonia + Ammonium UIA = Ammonia

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Water Quality and Chemistry

Filter Media

Inert
{all are mechanical}

Inert Rocks/Pebbles Sponge Wool Ceramic or special glass chips Membranes {eg Reverse Osmosis; removes selected molecules}

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Water Quality and Chemistry

Filter Media (or similar)

Active
{all are mechanical/ many will allow nitrogenous oxidising activity}

Peat or living moss {^acids; soften; ^ organic compounds} Plants {lower nitrates} Activated Carbon {catalyst; remove certain chemicals} Clay {softens; remove chemicals; add minerals} Calcium Carbonate chips {Redox & Alkalinity Buffer} ## Aluminium oxide or Ferric oxide base. {Phosphate} ## Denitrifying Modified Beds {Nitrate Removal}

Sulphur-source or Carbon-source added Deep anaerobic filter bed

# Zeolites/Molecular Sieves {remove ammonia etc; removes and exchanges various ions}
# = Care - nutrient hazard ## = Extra Care - toxic hazard
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Water Quality and Chemistry

Name a Seemingly Complicated Problem in Marine Aquaria?

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Water Quality and Chemistry

Calcium/ Magnesium/ Alkalinity/ pH

A Complex Convolution

Measurement Artifacts by not considering significance of changes.

Saturation of Calcium and solubility changes (Mg increases Ca Solubility) Incorporation of Magnesium and Strontium into Corals Ion-Pair interactions changing solubilities and pH Buffering

pH affecting solubilities

Nitrogen Cycle; Water Changes; Diurnal Changes; Carbon Dioxide..etc etc

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Water Quality and Chemistry

Calcium and Magnesium

Magnesium, Mg2+ (24.3g/mol)
Chemical Abundance in Seawater

Calcium, Ca2+ (40g/mol)

Soft Reactive Alkali-Earth Metals THIRD (1285ppm) FIFTH (420 ppm)

In Water
Biological Uses..

RedOx, Hardness (GH), Conductivity, Ionic Strength, ion-pair effects, SOLUBILITY, marine pH Buffering, (plus often associated in molecular form with Acid/Bases/Alkalinity)
Key Catalyst, Messenger Nerve impulses Nucleotide association (polyphosphates) eg DNA, RNA, ATP. Chlorophyll (a Magnesium porphyrin) And more Diabetes, migraines, osteoporosis, neurological (maybe depression). Alcohol lowers magnesium. Unbalanced protein intake inhibits magnesium absorption.. Coffee, Tea, Spices and Nuts, Green Veg., FISH FOOD !! Key Secondary Messenger. Nerve impulses Blood Clotting Cell Division Fertilisation Muscle action Immune Responses Regulator of Osmotic Stress. Bone Tetany (seen in cows), Rickets, etc Overfloading can cause excitotoxicity (eg after a stroke)

Health (deficiency)

Sources (examples)

Nuts, Milk, some green veg, shells.

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Water Quality and Chemistry

Calcium/ Alkalinity Balanced Additives

500 450 400 350 300 4.5 4 3.5 3
500 450 400 350 300 5 6 4

Ca2+

Ca2+

Alk

250 2 200 150 100 50 0 1 2 3 4 Tim e 5 6 7 1.5 1 0.5 0

250 200 150 100 50 0 1 2 3 4 Tim e 5 6 7

Ca2+ ppm

Alkalinity (meq/l)

Ca2+ ppm

Alkalinity (meq/l)

Calcium Steady; Alkalinity Crash ! (halves in a week)

Calcium Steady; Alkalinity Rise (doubles in a week)

Do NOT just increase Alkalinity

Probably too much Balanced Additive Reduce Balanced Additive

Increase BOTH calcium and Alkalinity Balance (1:1 formula)

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Alk

2.5

Water Quality and Chemistry

Summary
1. 2.

No amount of Knowldege can make up for poor Water Management. Water Chemistry is complex
Standard Text Book chemistry does not necessarily apply

3.

Water Chemistry is not an option. !!

You may not want to know it. But your Fish DO.

4. 5. 6. 7. 8.

Do not mess with Water Chemistry unless one understands the implications Understanding the complexity may help explain unexplained Know the requirements of your fish Linking the Science to the Experience will help develop Aquatic Husbandry Many apologies for use of technical or scientific terminology.it is not jargon and allows communication with a wider audience
Ian Millichip