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Water-
Quality and ChemistryLFKS
18 May 2011
Water Quality and Chemistry
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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
Water Quality and Chemistry
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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
Water Quality and Chemistry
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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 *
Water Quality and Chemistry
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Water Is
Oxidane
An Anomoly
Water Liquid at Room Temp Hydrogen Sulphide toxic gas
Selenium Hydride toxic flammable gas
Water Quality and Chemistry
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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)
Water Quality and Chemistry
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Water Is
Life
Cradle of Life
Vital Biochemical
Water to Oxygen
Oxygen to Water
Hydrolysis/Catalyst
Substrate
Destroys Cells
Water Quality and Chemistry
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Chemistry is aboutChanges
But Change cannot be anyold Change.
Chemistry in 3 Human Scenarios
Water Quality and Chemistry
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Change
Water Quality and Chemistry
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Change
Water Quality and Chemistry
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
Water Quality and Chemistry
l d h
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Getting Down to Business
Water Quality and Chemistry
W t Q lit d Ch i t
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Starting With Getting some water
Water Quality and Chemistry
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?
Water Quality and Chemistry
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
Water Quality and Chemistry
Wate Q alit and Chemist
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Ammonia + Chlorine + HCl Chloramines
Ian Millichip
RO System & Chloramines
Water Quality and Chemistry
~ 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)
Water Quality and Chemistry
Water Quality and Chemistry
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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)
Water Quality and Chemistry
Water Quality and Chemistry
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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
Water Quality and Chemistry
Water Quality and Chemistry
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Conductivity (and TDS ?)
Water Quality and Chemistry
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.
Water Quality and Chemistry
Water Quality and Chemistry
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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
Water Quality and Chemistry
Water Quality and Chemistry
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Methylene Blue
Water Quality and Chemistry
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
Water Quality and Chemistry
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Test Indicators
Water Quality and Chemistry
A pH Indicator (Thymol Blue)
General Hardness Indicator
Nitrte/Nitrate Test
Water Quality and Chemistry
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Test Kits (Hints)
Water Quality and Chemistry
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
Water Quality and Chemistry
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Test Kits (Hints)
Water Quality and Chemistry
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
Water Quality and Chemistry
Water Quality and Chemistry
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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.
Water Quality and Chemistry
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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
Water Quality and Chemistry
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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
Water Quality and Chemistry
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Name a SeeminglyComplicated Problem in
Marine Aquaria?
Water Quality and Chemistry
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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