Water Chemistry LFKS 18May

7/31/2019 Water Chemistry LFKS 18May

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Ian Millichip

Water-

Quality and ChemistryLFKS

18 May 2011

Water Quality and Chemistry


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Ian Millichip

Aims1. Emphasise the wonders of water and

some science of water.

2. De-mystify some parts of waterchemistry and show patterns

3. BUT.some bits will confuse evenmore!

4. Explain the meaning and Relationship ofcommon water quality parameters

5. Discuss the measurement and relation ofwater parameters to fish health

6. Set a platform for future study



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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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Some Food for Thought

(first)



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If the pH is acidic does all ammonia existas 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 howmuch acid is in the aquarium? NO *



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Water Is

Oxidane

An Anomoly

Water Liquid at Room Temp Hydrogen Sulphide toxic gas

Selenium Hydride toxic flammable gas



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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 Is

Life

Cradle of Life

Vital Biochemical

Water to Oxygen

Oxygen to Water

Hydrolysis/Catalyst

Substrate

Destroys Cells



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Chemistry is aboutChanges

But Change cannot be anyold Change.

Chemistry in 3 Human Scenarios



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Change



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Change


In Short..Chemistry is A downhillslippery and messy slopewith

Getting to Equilibriumand

Having MinimumEnergy AND

Giving out the MostUseable Energy

With the MaximumEntropy (=mess orchaos)

HIGH ENERGY

LOW ENERGY


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ChangeRule is:1/3 downstairs


l d h


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Getting Down to Business


W t Q lit d Ch i t


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Starting With Getting some water


R.O. Unit

Fish Tank

Water Conditioner

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

?? What is in it ??

W t Q lit d Ch i t


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What is in the Bucket?


W t Q lit d Ch i t


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Conditioners

DechlorinationSodium 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 Protectionaloe vera and other herbals

carboxymethylcellulose

Polyvinylpyrrolidone

Other Additives


Wate Q alit and Chemist


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Ammonia + Chlorine + HCl Chloramines

Ian Millichip

RO System & Chloramines


~ pH

Activated

Carbon(Low Peroxide No.)

pH > 7.5

Ammonia (UIA)

ToRO Unit

Ammonia + ^pHLower pH >AmmoniumAnd reduceMembrane

Swelling

RO Membrane



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Acids/Bases et alpHone of themeasures 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 weakbase

Alkalinity

Type of buffering. MEASURE..solutions ability to neutalise an acid.

Linked in Aquaria to Carbonate buffering (and hardness)




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HardnessClassically.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 isbeing 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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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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Conductivity (and TDS ?)


Carnegiella marthae (hatchetfish)

Chocolate Gourami

Pterophyllum altum

Symphysodon discus

Three-lined pencilfish

Cardinal tetra

Clown Loach

Dwarf Gourami

Ram CichlidSymphysodon 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

20-50 S/cm

50-100 S/cm

100-200 S/cm

Malawi CichlidsIndian glass fish

Firemouth & Convict Cichlid (and

some other Cichlosoma type

cichlids)

Platy & Swordtail

Most Rainbow Fish

White cloud mountain minnow

American Flag Fish (Jordanellafloridae)

Scatophagus argus

Celebes Rainbow Fish

Molly & Guppy

Goldfish

Tanganyikan Cichlid

> 500 S/cm

200-500 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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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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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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Methylene Blue


Key Treatment in Aquaria Stain for microscopy and clinicaldiagnosis

Redox Indicator **

Methaemoglobinaemia / CyanidePoisoning / Carbon MonoxidePoisoning **

** = my academic area of study

Photosensitiser Hepatitis C/ Kaposi's sarcoma/inactivates Staphylococcusaureus

Anti-Malarial Induces Cancer Cell Apoptosis ** Protects against Mustard AlkylatingAgent Neurotoxicity ** Mono Amine OxidaseInhibitorused to make anti-psychotic drugs **

RedOx Agent



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Test Indicators


A pH Indicator (Thymol Blue)

General Hardness Indicator

Nitrte/Nitrate Test



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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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Test Kits (Hints)


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

For probe-based equipmentMake 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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Which Are Acids and Bases?Aluminium chloride ACID Lobe-LUMO Lewis acids

Amm onia (NH 3) BASE Lobe-HOM O Lewis bases

Amm onium ion [NH 4]+

ACID Onium Ion Lewis acids

Benzene BASE HOMO Lewis bases

Calcium Ion (Ca2+

) ACID s-LUMO Lewis acids

Chlor ide (Cl-) BASE Lobe-HOM O Lewis bases

Cyanide (CN-) BASE Lobe-HOM O Lewis bases

Ferric (Iron III) chloride (FeC l3), ACID Lobe-LUMO Lewis acids

Ferric Ion (Fe3+

); Cupric Ion (Cu2+

); Ferrous Ion(F e

2+); Lead II ion (Pb

2+);

Si lver ion (Ag+)

ACID Heavy Metal Lewis acids

Hyd ride Ion (H-) BASE s-HOMO L ewis bases

Hydrogen (H 2) BASE s-HOMO L ewis bases

Hydrogen Ion or Proton (H+) ACID Proton Lewis acid

Hydroxide ion (OH-) BASE Lobe-HOM O Lewis bases

Magnesium Ion (Mg2+

) ACID s-LUMO Lewis acids

Me rcury (Hg ); Iron me tal (Fe) ACID Heavy Metal Lewis acids

Methane (CH 3) BASE Lobe-HOM O Lewis bases

Nitrite ion [NO 2]- BASE Lobe-HOM O Lewis bases

Oxonium ion [OH 3]+

ACID Onium Ion Lewis acids

Sodium ion (Na+) ACID s-LUMO Lewis acids

W ater (H2O ) BASE Lobe-HOM O Lewis bases




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Acids in Water

Q y y



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pH (Strong Acid)

Q y y

Grams HCl ~ pH

3700 1.00

1850 1.30

370 2.00

37 3.00

3.7 4.00

0.37 5.00

0.037 5.96

0.0037 6.70

0.00037 6.96

0.000037 7.00

0.0000037 7.00

0.00000037 7.00

0 7.00

1000 litres

HCl + Pure Water

Hyrogen Chloride (HCl)In water

= Hydrochloric Acid

(1 mole HCl = 36.5g)



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pH (Weak Acid)

Q y y

1000 litres

HAc + Pure Water

Acetic Acid (HAc)(1 mole HAc= 60g)

pKa = 4.75

Grams HAc ~ pH

6000 2.88

3000 3.03

600 3.38

60 3.88

6 4.38

0.6 4.88

0.06 5.37

0.006 5.85

0.0006 6.290.00006 6.63

0.000006 6.85

0.0000006 6.95

0 7.00

B



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pH (Weak Acid as Buffer)

Q y y

pKa1 2.1

pKa2 7.2

pKa3 12.4

Baseconj

A

Acidconj

H

Acid

HA aqaqaq

'')(

)()()(

}{

}}{{

HA

AH

Ka

)(10 aa KLogpK

)}{(10 aKHALogpH



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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 (mainlyby passive diffusion)

Diffusion of Ammonia out of fish depends on ammonia inoutside water and pH.



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Nitrogenous Compounds

Amino Acids / Waste / Dead fish / uneaten food

In the Aquarium

Ammonia (NH3)

Ammonification

[RAPID]

Nitrosofication(Nitroso-bacteria+Oxygen)

Nitrous Acid/Nitrites (NO2)

Nitrification(Nitro-bacteria+ Oxygen)

Nitric Acid/Nitrates (NO3)

0.06 mg/L

0.5 mg/L

90.0 mg/L



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Ammonia

Total Ammonia = Ammonia + AmmoniumUIA = Ammonia



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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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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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Name a SeeminglyComplicated Problem in

Marine Aquaria?



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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..etcetc



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Calcium and MagnesiumMagnesium, Mg

2+(24.3g/mol) Calcium, Ca

2+(40g/mol)

Chemical Soft Reactive Alkali-Earth Metals

Abundance

in Seawater

THIRD (1285ppm) FIFTH (420 ppm)

In

Water

RedOx, Hardness (GH), Conductivity, Ionic Strength, ion-pair

effects, SOLUBILITY, marine pH Buffering, (plus often

associated in molecular form with Acid/Bases/Alkalinity)Biological

Uses..

Key Catalyst, Messenger

Nerve impulses Nucleotide association

(polyphosphates) eg DNA,

RNA, ATP.

Chlorophyll (a Magnesium

porphyrin)

And more

Key Secondary Messenger.

Nerve impulses Blood Clotting

Cell Division

Fertilisation

Muscle action

Immune Responses

Regulator of Osmotic Stress.

Bone

Health

(deficiency)

Diabetes, migraines, osteoporosis,

neurological (maybe depression).

Alcohol lowers magnesium.

Unbalanced protein intake inhibits

magnesium absorption..

Tetany (seen in cows), Rickets, etc

Overfloading can cause excitotoxicity (eg

after a stroke)

Sources

(examples)

Coffee, Tea, Spices and Nuts, Green

Veg., FISH FOOD !!

Nuts, Milk, some green veg, shells.



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Calcium/ Alkalinity Balanced Additives

0

50

100

150

200

250

300

350

400

450

500

1 2 3 4 5 6 7

Time

Ca2+

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

Alk

Ca2+ ppm Alkalini ty (meq/l)

0

50

100

150

200

250

300

350

400

450

500

1 2 3 4 5 6 7

Time

Ca2+

0

1

2

3

4

5

6

Alk

Ca2+ ppm Alkalini ty (meq/l)

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

Do NOT just increase Alkalinity

Increase BOTH calcium andAlkalinity Balance (1:1 formula)

Calcium Steady; Alkalinity Rise(doubles in a week)

Probably too much Balanced Additive

Reduce Balanced Additive



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Summary1. No amount of Knowldege can make up for poor Water

Management.2. Water Chemistry iscomplex

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. Do not mess with Water Chemistry unless one

understands the implications5. Understanding the complexity may help explain

unexplained6. Know the requirements of your fish

7. Linking the Science to the Experience will help developAquatic Husbandry

8. Many apologies for use of technical or scientificterminology.it is not jargon and allows communicationwith a wider audience

Documents

Water Chemistry LFKS 18May