Water Chemistry

...for fun and profit!

With your host, Eddie Beuerlein

Introduction
IT Security Engineer
Scientific topics explored in-depth
Five years with hands-on aquaponics
Certifications:
Aquaponic Engineering & Design - Ryan Chatterson
Recirculating Aquaculture - Cornell University
Fish Health - U.S. Fish & Wildlife
Aquaculture/Aquaponics - University of Hawaii (ATOLL)
Fish Health for Producers - University of Wisconsin-Madison (School of
Veterinary Medicine)
Photovoltaic (PV) Solar - NABCEP
Contact info: eddie@havensec.com or 571-989-2884
Audience Questions

How many of you have an aquaponics set up at home?

Any full time or mostly full time farms?
Who lives in a humid environment?
Who here is limited in their aquaponics involvement by time?
Money? Space?
Anyone think aquaponics is hard?
Why should we care about water chemistry?
Ever wondered why your <insert crop here> doesnt look as good as someone
elses veggies?
Why wont my plants grow? Flowers? Produce?
Proactively prevent problems (fish health, plant health, system health etc.)
Control and prevent ongoing nutrient deficiencies - if you can see it, you have
already lost productivity
Reduce losses and increase yield - the holy grail
Plus... its fun! Pretty colors, droppers, test tubes, syringes - oh my!
Commercial vs Residential (Backyard)
Aquaponics
Commercial Residential

Water quality testing Very important Not as important

Growing veggies Selling for profit Enjoy fresh produce

Quality of produce Very important - may want Important but

to do leaf tissue analysis blemishes/deficiencies
won't affect bottom line

Philosophy on Required As needed/never

supplementing
Water quality parameters

Total nitrogen: Ammonia(NH4), Nitrite(NO2), Nitrate(NO3)

pH
Dissolved oxygen (DO)
CO2
Temperature
Water hardness: General hardness (GH) and carbonate hardness (KH) - also known
as alkalinity
Plant specific parameters: calcium, magnesium, potassium, phosphorous, iron,
sulfur and others (e.g. boron, silicate).
Water quality parameters continued...
General safe ranges for fish and plants and bacteria:
Ammonia: 0 ppm (dependent on pH)
Nitrite: 0 ppm
Nitrate: 0-150 ppm (can be higher but may cause fish health issues)
pH: 6-8
DO: 5-8 ppm
Temperature: 68-90F (can depend on DO and fish species)
Where is your source water from?

Tap
Pay attention to chlorine/chloramines
Chlorine can be outgassed using aeration/bubbler for 24hrs
Chloramines can be removed using the following: UV, activated carbon,
vitamin C, sodium thiosulfate (preferred), other methods (boiling and
superchlorination are not viable for aquaponics)
Check your local water companys annual water quality report
Well
pH can change once exposed to air - usually rises as CO2 leaves the water
Can contain nitrates, sulfur, CO2 etc. so testing is important to determine
impact
Source water (cont.)

Surface water can contain bacteria/viruses and other pollutants

Rain
Usually lower in pH due to CO2 dissolved in it and less minerals dissolved
Can contain heavy metals depending on roofing material - not recommended
with shingled roofs
Contamination from animal waste (birds)
Best if used with an activated carbon filter to help lower heavy metals and
other pollutants
Testing Your Water

API Freshwater Master Test Kit

Everyone should know and use this kit (or one like it)!
$22 from Amazon
What does it test?
Ammonia, nitrite, nitrate, and pH
What should I test with?
Source water (VERY IMPORTANT)
Aquaponics system water
When should I test?
Reading too high? Use dilution to find the real value. 2-fold - means add 2.5mL of
distilled water + 2.5mL of system water. Then multiply results by 2.
Getting Water Tested For You

Available from some universities (U of Minnesota, U of Florida, etc.)

Water quality testing companies - often called an irrigation water test
Usually costs from $40-80 per sample - so shop around to get best price
8oz water bottle filled with tap or source water works for most companies
Dont forget to label the bottles in order to interpret results properly!
Lesser Known Water Quality Tests

These tests can be just as important as the API kit. Think of the API kit as being the
minimum height required to ride the roller coaster!
Alkalinity (KH) - measures carbonate buffer (helps to control pH swings)
General Hardness (GH) - related to alkalinity and useful for measuring
calcium/magnesium
KH and GH test kits can be purchased from API
Gas tests: Dissolved Oxygen (DO) and CO2 (can affect pH)
Nutrient tests: iron, calcium, magnesium, sulfate, boron, manganese, etc - how do
I test these?
Water quality testing methods
Ranked by cost/effectiveness:
Titration tests - commonly used: API freshwater test kit, API KH/GH, etc
Pens - used for pH and measuring specific nutrients like potassium
Sensor based - DO meters, pH meters, etc
Colorimeters - similar to titration tests but provide a digital readout (tend to be
more accurate than titration)
ICP - Inductively coupled plasma mass spectrometer - universities and commercial
water testing facilities are only ones that can afford these.
Commercial aquaponics systems should have a good pH and DO meter (around $500)
and a multi-test colorimeter ($1600-$2100 plus reagent costs).
Water quality testing methods (continued)

For those of you who are smaller or midsize I would recommend:

Lamotte ColorQ Pro-7 colorimeter (~$200)
Can test pH (6.5 - 8.5)
Total alkalinity (0-250 ppm) - useful for monitoring pH buffer
Calcium hardness (0-700 ppm) - can be used to calculate calcium and magnesium levels
Chlorine - useful for detecting chloramines
IOrodeo colorimeter (~$100)
Arduino based, new tests can be uploaded, kit - some minor assembly required
Tests: ammonia, nitrite, nitrate, iron, potassium, phosphate, sulfate and newly added
pH!
I am working with IORodeo to add new tests - calcium hardness is next (so you wont
need the Lamotte tester)
InFocus - pH and Temperature

Most important water quality measurement - pH (generally recognized as power

of hydrogen)
When the ratio of H+ and OH- ions is equal then pH is neutral (7.0)
Complex relationship with most other water chemistry parameters
Logarithmic scale of 10 - this means a change from pH of 8.0 to 6.0 is (10x10 =100)
times difference in acidity or basicity. Range is ~0-14.
When adjusting, try to not change more than .2 - .4 per day.
In aquaponics, shoot for pH of 6.5-6.8 for best nutrient availability without
compromising fish/bacteria health (7.0 is fine but you will see some nutrient
issues).
pH and Temperature continued...

Test on a regular basis and monitor closely when pH gets close to 6.

Biological filtration is negatively impacted once pH drops below 6.
Alkalinity has a large impact on pH.
Temperature
Dramatic impact on fish/bacteria/plants if allowed to fluctuate. Be careful with
extreme changes when growing outdoors. Media beds combined with flood and
drain can cause temperature swings.
Can lead to dangerous ammonia levels.
Try to keep in the sweet spot for fish/plants - heaters are advised
TAN/Temperature/pH chart
InFocus - Ammonia, Nitrite, Nitrates

Easily tested with API test kit - reading colors can be tricky though
Ammonia/nitrites are deadly to fish and bacteria in too high levels
Ammonia: impact is highly dependent on pH and temperature levels - refer to
chart - too much can affect cycling time (> 5 ppm)
Nitrites: more than 2 ppm can be deadly but can be mitigated using NaCl (salt)
Nitrates:
Contrary to popular belief high nitrates (over 150 ppm) cause issues with fish
- one of many stressors
High nitrates will prevent large amount of fruiting on plants such as tomatoes,
cucumbers, peppers, etc (over 80 ppm)
InFocus - Total Hardness and Alkalinity

Hardness is a confusing term - total, permanent and general hardness are all the
same thing
Even more confusing - measured in a variety of units: dGh, ppm, mmol/L, gpg, etc
Usually expressed as CaCO3 (calcium carbonate)
Permanent hardness is mineral content that cant be removed by boiling, usually
comprised of sulfate or chloride compounds (Ca/Mg)
Alkalinity refers to carbonate hardness (dKh/ppm)
Also known as temporary hardness since it can be removed via boiling
There are other metals that can affect hardness so make sure to test water
General Hardness
(GH) API test:

9 drops = 160 ppm

CaCO3

Carbonate hardness
(KH) API test:

7 drops = 125 ppm

CaCO3
Total Hardness and Alkalinity continued...

Formula: Total permanent hardness = calcium hardness +

magnesium hardness
Total permanent hardness (CaCO3) = 2.5(Ca2+) + 4.1(Mg2+)
Ca2+ and Mg2+ are the ionic form - most water tests return
results in CaCO3
Formula is useful for calculating magnesium numbers in your
system water. Use GH test results and a method for testing
calcium hardness (Taylor test or colorimeter).
Using the Total Hardness formula (example)

Formula reminder: Total Permanent Hardness (CaCO3) = 2.5(Ca2+) +

4.1(Mg2+)
You have run your GH API test and the color turned in 18 drops (18 dKH).
You tested your water using the Taylor Calcium test: 200 ppm CaCO3
So: 18 dKH = 321.4 ppm CaCO3
To find magnesium, adjust formula: Mg hardness = Total hardness - Ca
hardness
Mg2+ = 321.4 ppm CaCO3 - 200 ppm CaCO3 = 121.4 ppm CaCO3
Your system has: 80 Ca2+ppm (200 / 2.5) and 29.6 Mg2+ppm (121.4 / 4.1)
InFocus: Iron

Essential component in production of chlorophyll

Iron is usually in two forms
ferrous(Fe2+) - plant available - soluble
ferric (Fe3+) - commonly called rust, oxidized iron, not plant available -
insoluble
pH affects the availability of the forms - higher pH means more ferric
Chelation allows the metal ions to be in a soluble form by binding to an amino
acid, organic acid (humic) or polyphenols (there are other types).
Dont use FeEDTA - toxic, used as an herbicide, only effective up to pH of 6.4
FeDTPA (effective up to pH of 7.5) or FeEDDHA (effective up to ph of 9) are best
InFocus: Iron (continued)

Best to maintain 2 mg/L (ppm)

usually added every 2-3 weeks but best to test and add as needed.
Most chelated irons will change color of your system water - this can affect
readings from colorimeters/titrations so make sure not to add too much
Calculate how much to add (assuming no iron in system and 6% iron DTPA):
2 mg/L = 7.56 mg/gal -- conversion factor
7.56 mg/gal / 0.06 mg pure iron/mg powder = 126 mg powder/gallon
For 300 gallon system, add: 126 mg * 300 gallons = 37800 mg or 1.33 oz every 2-3
weeks.
InFocus: NaCl (table salt)
Useful for reducing nitrite poisoning in fish
Nitrite poisoning is known as brown blood disease - affects ability for fish to uptake
oxygen from water
Nitrite oxidizes the hemoglobin into methemoglobin, which cannot uptake oxygen
1 - 2 parts per thousand (ppt) or 9:1 (chloride:nitrite) for protection against nitrite
poisoning
Fish sick?
You can use salt to cure a bunch of diseases and parasites without use of
antibiotics/antifungals
Increase your system to no more than 3-4 ppt or plants will get affected (strawberries
affected above 1 ppt)
Make sure the salt doesnt have anti-caking additives
Use pool salt or water softener salt (not the iron reducing kind)
Dont confuse epsom salt (MgSO47H20) with table salt (NaCl)
InFocus: NaCl (table salt) (cont)

Test using salinity refractometer or pen probe

Calculation:
How much salt to add for 2ppt (2 kg/1000L = 2 ppt)?
In a 300 gallon system (1135.62L):
2kg/1000L = x/1135.62L
1000x = 2271.24
X = 2.3 kg or 81 oz. or 5 pounds of salt
Lowering your pH

Often high pH a problem when first getting a system fired up

Check your Source water as first step
high pH indicates a challenge
higher pH does allow for biological filter to ramp up quicker (pH of 7+)
Nitrification naturally lowers the pH over time but this can take a while!
Try not to lower pH more than .2-.4 per day - this is to avoid stressing fish.
Calculating impact of acid additions is very complex due to variety of
buffers present in system water (would have to measure every buffer
type, pHa for each, etc.)
Lowering pH (cont)
Options for lowering pH:
Add reverse osmosis (RO) water
Pros: easy to purchase, can buy RO water from many fish stores
Cons: equipment can be expensive ($200+), wastes a decent amount of water, water
lacks any chemical compounds so you will have to add some back which can increase
overall costs
Add rainwater (tends to be acidic due to CO2 and lack of buffers)
Pros: easy to collect, easy to measure pH
Cons: might contain other pollutants (heavy metals from roofing material, bird waste,
etc.)
Add acid to top up water (dont add directly to system water!)
Pros: relatively easy and effective, cost is somewhat variable depending on acid choice
Cons: can add other elements that might not be desirable, so do it slowly!
Reverse Osmosis Rain water Acid
Lowering pH (cont)

***SAFETY WARNING*** - acids are dangerous!

Always add acid to water SLOWLY!
Always use eye, hand, & body protective wear
Acids that can be used to lower top up water pH:
Nitric acid (H2NO3) - will add nitrates
Hydrochloric acid (HCl) - will add chlorides
Phosphoric acid (H3PO4) - will add phosphates
Sulfuric acid (H2SO4) - will add sulfates
The acids will react with the carbonates in the water - in order for the pH to drop, the
carbonates (and bicarbs) will need to be used up (converted to CO2)
Acids and carbonates

These are just examples since everyones top up water could contain any mix
of calcium, magnesium, zinc, and other carbonates:
2HCl + CaCO3 = CaCl2 + CO2 + H2
2HCl + MgCO3 = MgCl2 + CO2 + H2O
H2SO4 + CaCO3 = CaSO4 + CO2 + H2O
2HNO3 + CaCO3 = Ca(NO3)2 + CO2 + H20
Alkalinity Calc is useful for estimating amount of acid needed:
https://extension.unh.edu/Agric/AGGHFL/alk_calc.cfm
Buffering your system
Nitrification naturally lowers the pH
Easy way to add supplements and buffer at same time!
Buffer is a mixture of weak acids and their conjugate bases that resist changes
in pH
Lots of choices - which ones should I use? Carbonate buffers to the rescue!
Phosphate can be used as a buffer but can lead to toxicity issues depending
on pH
Carbonate buffer system is complicated and wont be reviewed here
Lets rank according to strength: hydroxides, carbonates, bicarbonates
Hydroxides are not usually considered buffers but often used to increase pH
Increasing the amount of carbonates/bicarbonates in the water increase alkalinity
and pH goes up
Buffering your system (cont.)
Common ways to buffer your system:
Hydroxides
Calcium [Ca(OH)2] and potassium hydroxides [KOH]
Very strong bases (pH of 12+)
Raises pH but not usually alkalinity
Ca(OH)2 - commonly called slaked lime or hydrated lime
KOH - commonly called caustic potash
Carbonates
pH of ~ 11
Calcium and Magnesium carbonates are commonly used
Dolomitic lime (AgLime) is typically comprised of Calcium/Magnesium
carbonates and hydroxides
Potassium carbonate - useful for potassium supplementation
Buffering your system (cont.)
Bicarbonates
pH of ~ 10
Potassium bicarbonate is most useful bicarbonate for aquaponics
Can be used as a fungicide such as for combating powdery mildew
Sodium bicarbonate can be used in an emergency for helping with biological
filters and fish but use it sparingly since it can easily contribute plant nutrient
deficiencies since sodium competes with calcium, magnesium, potassium and
ammonium.
All buffers should be added slowly and on a regular basis depending on your
feeding levels and pH.
For commercial setup, you may want to consider using a peristaltic pump for
constant addition (coupled with a pH meter).
Macro and micro nutrients

Out of a total of 92 natural minerals, only 60 have been found in various plants. 16
of those 60 have been deemed essential.
The 16 have been divided into those required in large amounts (macro) vs. trace or
minor amounts (micro).
Macro: carbon (C), hydrogen (H), oxygen (O), nitrogen (N), phosphorus (P),
potassium (K), calcium (Ca), sulfur (S), and magnesium (Mg).
Micro: iron (Fe), chlorine (Cl), manganese (Mn), boron (B), zinc (Zn), copper (Cu),
and molybdenum (Mo).
Supplementation Guidelines

Iron (Fe): 1-2 ppm

Calcium (Ca): 40-150 ppm
Magnesium (Mg): 40-70 ppm
Potassium (K): 40-100 ppm
Phosphorus (P): 10-20 ppm (light feeders), 20-40 ppm (heavy feeders)
Nitrate (NO3): 1-80 ppm
Common nutrient ratios (to help avoid lockout - pH needs to be in 6.3-6.8 range):
Ca/Mg - 2:1 to 4:1 (preferable on the higher side)
Ca:P - 3:1 to 4:1
Ca:K - 1:1 to 2:1
Supplement calculations

On previous slide, there is nutrient ratio for Ca2+/Mg2+ of 2:1.

If Ca = 56 ppm and Mg = 22.5 ppm, how much Mg is needed to
be added to maintain the ratio (56/22.5 = 2.5:1)?
1. 56/x = 2/1
2. 2x=56
3. x=28
28ppm Mg - 22.5ppm Mg = 5.5 ppm of Mg needed
Supplement calculations - part 2

Lets use epsom salt to supplement Magnesium (Mg2+): MgSO4 7H2O

Atomic mass of Mg: 24.305
Atomic mass of S: 32.066
Atomic mass of O: 15.999
Atomic mass of H: 1.008
Total mass of MgSO4 = 24.305 + 32.066 + 4(15.999) = 120.367
Total mass of 7H2O = 7(1.008 x 2) + 15.999)) = 126.105
Total atomic mass of MgSO4 7H2O = 120.367 + 126.105 = 246.5
Supplement calculations - part 3

From last slide, remember: MgSO4 7H2O = 246.5 atomic mass

1.24.3 mg of Mg / 246.5 mg of MgSO4 = 5.5 mg Mg / X (solve for
X by cross multi)
2.24.3x = 1355.75
3.X = 55.8 mg of MgSO4 7H2O
So, by adding 55.8 mg of MgSO4 7H2O per 1 Liter of water, you
will add 5.5 mg of Mg2+.
Supplement calculations - part 4

Assume your system has 300 gallons of water (1135.6 Liters).

Then, 55.8 mg of MgSO4 7H2O x 1135.6 L = 63366.48 mg or 63.4 grams
(~4 tablespoons) needed to be added to the system.
Now, on your own, figure out how much sulfate is added at the same time
And?
Advanced calculations (not always needed):
calculate increased amount needed depending on purity (example shown in the
iron calculation)
solubility calculations