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ALKALINITY AND HARDNESS

Chemical Variables:
Total Alkalinity
Total Alkalinity: the total amount of titratable

bases in water expressed as mg/L of equivalent


CaCO3.
Alkalinity is primarily composed of the following
ions: CO3-. HCO3-. hydroxides. ammonium. borates.
silicates. phosphates.
Alkalinity in ponds is determined by both the quality
of the water and bottom muds.
Calcium is often added to water to increase its
alkalinity. buffer against pH changes.

Total Alkalinity
Total alkalinity = 200 mg/L. Good buffering capacity of

a water source.
Freshwater 5 mg/L (soft water) to 500 mg/L (hard

water).
Seawater ~ 115-120 mg/L.
Seldom see pH problems in natural seawater.
Alkalinity < 30 mg/L? Problem?

Total Alkalinity
Total Alkalinity (TA) level can be associated with several
potential problems in aquaculture:
If TA< 50 mg/L: copper compounds are more toxic.
avoid their use as algicides (copper sulfate)
Natural waters with less than 40 mg/L alkalinity as
CaCO3 have limited biofiltration capacity. pH
independent (What does this mean?)
Low alkalinity = low CO2 --> low natural productivity
Low alkalinity equals low pH.

Total Hardness
Total Hardness: total concentration of metal ions

expressed in terms of mg/L of equiva- lent CaCO3.


Primary ions are Ca2+ and Mg2+. also iron and
manganese.
Total Hardness approximates total alkalinity.
Calcium is used for bone and exoskeleton formation
and absorbed across gills.
Soft water = molt problems.
bone deformities....
or minimally...clogged pipes!

CONVERSION OF WATER HARDNESS UNITS

Water Hardness Internatio Physical America & English


oe
Unit
nal
measures states
Definition
recomme mval/liter
PPM
nded
mmol/liter

French
of

German
odH

100mg CaCO3 28 mg CaO or 1 part CaCO3 1 grainCaCO3 10 mg/ CaCO3 10 mg/CaO


per 1000 ml 50 mg CaCO3 per million = 1 per gallon= per 1000 ml per 1000 ml
water
per 1000 ml
mg CaCO3
14.3 mg
water
water
water
per 1000 ml
CaCO3 per
water
1000 ml water

1 mmol/litre

100

7.0

10.00

5.6

1 mval/litre

0.5

50

3.5

5.00

2.8

1 PPM

0.01

0.02

0.070

0.10

0.056

1 Oe

0.1429

0.285

14.29

1.429

0.7999

1 Of

0.10

0.20

10.00

0.700

0.5599

1 OdH

0.1786

0.357

17.86

1.250

1.786

DEGREE OF HARDNESS EXPRESION


SOFT: < 1.6 mmol/l = 160 PPM = 9 odH
SLIGHTLY HARD: 1.6-3.2 mmol/l = 160-320 PPM = 9-18 odH
HARD: 3.2-4.6 mmol/l = 320-460 PPM = 18-26 odH
VERY HARD: ABOVE 4.6 mmol/l = ABOVE 460 PPM =
ABOVE 26 odH

Chemical Variables:

pH

pH: the level or intensity of a substances acidic


or basic character.

pH: the negative logarithm of the hydrogen ion


concentration (activity) of a substance.
pH = -log(1/[H+]).

Ionization of water is low (1x10-7 moles of H+/L


and 1x10-7 moles OH-/L).
Neutral pH = similar levels of H+ and OH-

Chemical Variables:

pH

At acidic pH levels. the quantity of H+ predominates.


Acidic pH = pH < 7. basic = pH >7
Most natural waters: pH of 5-10. usually 6.5-9;
however. there are exceptions.
Acid rain. pollution.
Can change due to atm. CO2 , fish respiration.
pH of ocean water is stable (carbonate buffering
system. later).

Chemical Variables:

pH

Other sources of change:


Decay of organic matter.
Oxidation of compounds in bottom sediments.

Depletion of CO2 by phytoplankton on diel basis.


Oxidation of sulfide containing minerals in bottom soils

(e.g.. oxidation of iron pyrite by sulfide oxidizing bacteria


under anaerobic conditions).

Chemical Variables:
Carbon Dioxide
Normal component of all natural waters.
Sources: atmospheric diffusion. respiration of
cultured species. biological oxidation of organic
compounds.
Usually transported in the blood as HCO3 Converted to CO2 at the gill interface. diffusion
into medium.
As the level of CO2 in the medium increases. the
gradient allowing diffusion is less.

Chemical Variables:
Carbon Dioxide
This causes blood CO2 levels to increase. lowering
blood pH.
With lower blood pH. carrying capacity of

hemoglobin decreases. also binding affinity for


oxygen to hemoglobin.
This phenomenon is known as the Bohr-Root
effect.
CO2 also interferes with oxygen uptake by eggs and
larvae.

CO2 Level Affects Hemoglobin


Saturation

Chemical Variables:
dioxide

carbon

In the marine environment. excesses of CO2 are

mitigated by the carbonate buffering system.


CO2 reacts with water to produce H2CO3. carbonic
acid.
H2CO3 reacts with CaCO3 to form HCO3(bicarbonate) and CO32- (carbonate).
As CO2 is used for photosynthesis. the reaction shifts
to the left. converting bicarbonates back to CO2.
What large-scale implications does this have?

The Effect of pH on
Carbonate Buffering

Chemical Variables:
dioxide
Concentrations of CO2 are

small. even though it is


highly soluble in water
inverse relationship
between [CO2] and
temperature/salinity
thus. CO2 solubility depends
upon many factors

carbon

Chemical Variable:
Carbon Dioxide
CO2 is not particularly toxic to fish or
invertebrates. given sufficient D.O. is available.

Maximum tolerance level appears to be around


50 mg/L for most species.
Good working level of around 15-20 mg/L.

Diel fluctuation opposite to that of D.O.


Higher levels in warmer months of year.

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