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

Ian Millichip

Water Quality and Chemistry

Some Food for Thought (first)

Ian Millichip

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 * Ian Millichip .

Water Quality and Chemistry Water Is… Oxidane  An Anomoly  Water Liquid at Room Temp  Hydrogen Sulphide toxic gas  Selenium Hydride toxic flammable gas  Ian Millichip .

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)  Ian Millichip .

Water Quality and Chemistry Water Is…  Life Cradle of Life  Vital Biochemical  Water to Oxygen  Oxygen to Water  Hydrolysis/Catalyst  Substrate  Destroys Cells  Ian Millichip .

Water Quality and Chemistry Chemistry is about Changes But Change cannot be any old Change. Chemistry in 3 Human Scenarios Ian Millichip .

Water Quality and Chemistry Change Ian Millichip .

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”) Ian Millichip .Water Quality and Chemistry Change HIGH ENERGY In Short……..

Water Quality and Chemistry Change – Rule is: 1/3 downstairs Ian Millichip .

Water Quality and Chemistry Getting Down to Business Ian Millichip .

O.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. Unit ?? What is in it ?? Fish Tank Ian Millichip .

Water Quality and Chemistry What is in the Bucket? Ian Millichip .

but not all.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. Organic or Synthetic Chelating agents.  Slime Coat “Protection” aloe vera and other „herbals‟  carboxymethylcellulose  Polyvinylpyrrolidone   Other Additives Ian Millichip .

) RO Membrane Ian Millichip pH > 7.5 .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.

 Linked in Aquaria to Carbonate buffering (and hardness)  Ian Millichip .solutions ability to neutalise an acid. MEASURE.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.Water Quality and Chemistry Acids/Bases et al  pH – one of the measures of acidity/basicity . 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.

”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….Water Quality and Chemistry Hardness Classically….  Different units used in different test (DH.   GH and KH are NOT chemically or mathematically related.depends exactly on what is being measured by a Test Kit.. “KH” vs “GH”…. Clarkes) Ian Millichip . ppm.

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  Ian Millichip .

Water Quality and Chemistry Conductivity (and TDS ?) Carnegiella marthae (hatchetfish) 20-50 μS/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.. Changing pH (up/down).messing  Changing Hardness  Balancing Alkalinity. Ghostfish Neon Tetra Most Corydoras Kribensis Cichlid Red piranha Rosy barb Siamese fighting fish Three-spot gourami Zebra Danio 200-500 μS/cm 50-100 μS/cm > 500 μS/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 μS/cm Conductivity Affected by…. Mg and Ca etc  Topping up water/ lack of water changes  Ian Millichip ..

+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.  Complex  RedOx Potential (ORP)  Potential to Donate Electrons (Reducing Environment)  Potential to Accept Electrons (Oxidising Environment)  Is just a measure (and ask…what is measured?)  +300 (Ox) to -100(Red) mV (marine).  Regular Partial Water changes.  Ian Millichip . good aeration  Having a good buffer  Monitoring and maintain pH. Alkalinity.Water Quality and Chemistry RedOx RedOx = Reduction and Oxidation  RedOx Balance is vitally important. Hardness help.

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  Ian Millichip .

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 Inhibitor…used to make antipsychotic drugs **  Ian Millichip .

Water Quality and Chemistry Test Indicators A pH Indicator (Thymol Blue) Nitrte/Nitrate Test General Hardness Indicator Ian Millichip .

 Do not cross-use (cross-contaminate) test phials   View test-results in good light Be aware that test kits are not 100% accurate. Take special note if aquarium water is tinted  If using drop-by-drop count. Store as directed  Keep ALL documentation  Use a syringe to measure water sample. and are 100% specific.Water Quality and Chemistry Test Kits (Hints) Take Note of Best Before Date. let drops simply „drop‟  Ian Millichip .

soak phials in distilled vinegar and rinse in RO/DI water.Water Quality and Chemistry Test Kits (Hints) Thoroughly clean all phials immediately after use 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? Ian Millichip  . and dry phials  Monthly.

L e a d II io n (P b ). 3+ 2+ F e rric Io n (F e ).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 ). 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 π – 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 Ian Millichip . C u p ric Io n (C u ). + 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 ). F e rro u s Io n 2+ 2+ (F e ).

Water Quality and Chemistry Acids in Water Ian Millichip .

0037 0.00 1000 litres 0.7 ~ pH 1.37 0.5g) Grams HCl 3700 1850 370 37 3.00 HCl + Pure Water 0.00 1.96 7.30 2.00037 0.037 0.00 7.00 3.96 6.000037 5.00000037 0 Ian Millichip 7.70 6.00 5.0000037 0.Water Quality and Chemistry pH (Strong Acid) Hyrogen Chloride (HCl) In water = Hydrochloric Acid (1 mole HCl = 36.00 7.00 4.00 .

000006 0.06 0.85 HAc + Pure Water 0.38 4.6 0.03 600 60 3.88 5.85 6.00006 6.95 7.37 5.38 3.00 1000 litres 0.29 6.Water Quality and Chemistry pH (Weak Acid) Acetic Acid (HAc) (1 mole HAc= 60g) pKa = 4.006 B 0.88 6 4.63 6.88 3.75 Grams HAc 6000 3000 ~ pH 2.0006 0.0000006 0 Ian Millichip .

1 7.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 2.2 12.4 Ian Millichip .

 „Surplus‟ amino acids need to be excreted…depends upon the body‟s water demands and supply.  Ian Millichip .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.  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.

5 mg/L Nitrosofication (Nitroso-bacteria + Oxygen) Nitrification (Nitro-bacteria + Oxygen) Nitric Acid/Nitrates (NO3) 90.06 mg/L Nitrous Acid/Nitrites (NO2) 0.Water Quality and Chemistry Nitrogenous Compounds In the Aquarium Amino Acids / Waste / Dead fish / uneaten food Ammonification [RAPID] Ammonia (NH3) 0.0 mg/L Ian Millichip .

Water Quality and Chemistry Ammonia Total Ammonia = Ammonia + Ammonium UIA = Ammonia Ian Millichip .

removes selected molecules}  Ian Millichip .Water Quality and Chemistry Filter Media  Inert {all are mechanical} Inert Rocks/Pebbles  Sponge  Wool  Ceramic or special glass chips  Membranes {eg Reverse Osmosis.

Water Quality and Chemistry Filter Media (or similar) Active {all are mechanical/ many will allow nitrogenous oxidising activity} Peat or living moss {^acids. remove chemicals. add minerals}  Calcium Carbonate chips {Redox & Alkalinity Buffer}  ## Aluminium oxide or Ferric oxide base. removes and exchanges various ions} # = Care .nutrient hazard ## = Extra Care . {Phosphate}  ## Denitrifying Modified Beds {Nitrate Removal}  Sulphur-source or Carbon-source added  Deep anaerobic filter bed   # Zeolites/Molecular Sieves {remove ammonia etc. remove certain chemicals}  Clay {softens.toxic hazard Ian Millichip . ^ organic compounds}  Plants {lower nitrates}  Activated Carbon {catalyst. soften.

Water Quality and Chemistry Name a Seemingly Complicated Problem in Marine Aquaria? Ian Millichip .

Carbon Dioxide. 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..etc etc Ian Millichip .Water Quality and Chemistry Calcium/ Magnesium/ Alkalinity/ pH A Complex Convolution     Measurement Artifacts by not considering significance of changes.

Ca2+ (40g/mol) Soft Reactive Alkali-Earth Metals THIRD (1285ppm) FIFTH (420 ppm) In Water… Biological Uses. RedOx. ion-pair effects. Conductivity. ATP.  Chlorophyll (a Magnesium porphyrin)  And more… Diabetes. Tea. osteoporosis. RNA.. FISH FOOD !!  Key Secondary Messenger.Water Quality and Chemistry Calcium and Magnesium Magnesium. Unbalanced protein intake inhibits magnesium absorption. Green Veg. SOLUBILITY... neurological (maybe depression).  Bone Tetany (seen in cows). Hardness (GH). Coffee. Messenger  Nerve impulses  Nucleotide association (polyphosphates) eg DNA. Mg2+ (24. Alcohol lowers magnesium.3g/mol) Chemical Abundance in Seawater Calcium. Milk. marine pH Buffering. Ionic Strength. migraines. shells. etc Overfloading can cause excitotoxicity (eg after a stroke) Health (deficiency) Sources (examples) Nuts. (plus often associated in molecular form with Acid/Bases/Alkalinity)  Key Catalyst. Rickets. some green veg. Ian Millichip . Spices and Nuts.  Nerve impulses  Blood Clotting  Cell Division  Fertilisation  Muscle action  Immune Responses  Regulator of Osmotic Stress.

5 4 3. 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) Ian Millichip Alk 2. Alkalinity Crash ! (halves in a week)    Calcium Steady.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.Water Quality and Chemistry Calcium/ Alkalinity Balanced Additives 500 450 400 350 300 4.5 .5 1 0.5 0 250 200 150 100 50 0 1 2 3 4 Tim e 5 6 7 3 2 1 0 Ca2+ ppm Alkalinity (meq/l) Ca2+ ppm Alkalinity (meq/l) Calcium Steady.

2.Water Quality and Chemistry Summary 1. 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…. 5. !! You may not want to know it.it is not jargon and allows communication with a wider audience Ian Millichip .   Water Chemistry is not an option. 7. 8. Water Chemistry is complex Standard Text Book chemistry does not necessarily apply 3. 4.  No amount of Knowldege can make up for poor Water Management. But your Fish DO. 6.