Properties of Water

LECTURE 3
Phase Diagrams
A phase in a material is a region that differ
in its microstructure and or composition
from another region
 homogeneous in crystal structure and
atomic arrangement
 have same chemical and physical
properties throughout
 have a definite interface and able to be
mechanically separated from its
surroundings
Phase Diagram of water
Chemical Properties: Dissolved Oxygen
(DO)
 Along with temperature, dissolved oxygen (DO), is
important in metabolic regulation.
 Dissolvedoxygen concentration and temp both
determine the environmental niche aquaculture
organisms occupy.
 Occupation of niches is controlled by a complex set
of behavioral and physiological (acclimatorial)
activities.
 Acclimation is slow with D.O. (hours, weeks)
Chemical Properties: Dissolved Oxygen
(DO)
 although oxygen is rather abundant in the atm (21%),
it is only slightly soluble in water (6 mg/L is not much)
 implications to fish/invertebrates
 Even metabolic rates of aqua-communities can effect
rapid changes in DO.
 this effect increases with temp (interaction)
 solubility decreases with increased temp/sal
 other factors: BP (direct), altitude (indirect), impurities
(indirect)
Chemical Properties: Dissolved Oxygen
(DO)

Oxygen solubility
curve
Chemical Properties: Dissolved Oxygen
(DO)
Factors affecting D.O. consumption:
Water temperature (2-3x for every 10oC).
Environmental (medium) D.O. concentration
(determines lower limit).
Fish size (Respiration greater for small vs. large).
Level of activity (resting vs. forced).
Post-feeding period, etc. (2x, 1-6 hrs post feeding).
Chemical Varibles: Dissolved Oxygen (DO)
 What might be considered
minimal levels of maintenance of
D.O.
 Hard to determine due to
compounding effects (can’t
standardize conditions).
 Major factor: exposure time
 For most species:
 long-term: 1.5 mg/L
 medium term: 1.0 mg/L
 short-term: 0.3 mg/L
Chemical Varibles: Dissolved Oxygen (DO)

 Ingeneral warm-water species are more tolerant of

low D.O. concentrations
 Ictalurus punctatus: adults/1.0 mg/L, fingerlings 0.5
mg/L
 Procamberus clarkii: adults/2.0 mg/L, juveniles/1.0
mg/L
 Litopenaeus vannamei: adults/0.5-0.8 mg/L
 Litopenaeus stylirostris: adults/1.2-1.4 mg/L
Chemical Varibles: Dissolved Oxygen (DO)
 Many practical aqua-culturists will recommend that
D.O. concentrations do not drop below 6.0 mg/L.
 Thisis an impractical guideline in that this level can
seldom be achieved at night.
A more practical guideline might be to maintain D.O.
levels around 90% saturation.
 No lower than 25% saturation for extended periods
Chemical Varibles: Dissolved Oxygen (DO)

 IfD.O. levels in the medium are adequate, fish meet

increased demands due to locomotion or post-
feeding by increased rate of ventilation or large
“gulps” of water.
 Declining D.O.: seek zones of higher D.O., reduce
activity (reduced MR), stop consumption of feed.
 Compensatory point: when D.O. demand cannot be
met by behavioral or physiological responses.
Chemical Variables: Dissolved
Oxygen/behavior
 Uponreaching compensatory point: gaping at surface,
removal of oxygen from surface.
 Shown in both fish and invertebrates.
 Small aquatic animals are more efficient.
 Someoxygen provided by glycolysis or anaerobic
metabolism, but blood pH drops.
 pH
drop in blood reduces carrying capacity of
hemoglobin (hemocyanin)--> death.
Chemical Varibles: Dissolved Oxygen (DO)
 Oxygen/Temperature
Interaction
 Oxygen consumption
increases with temperature
until a maximum is
achieved.
 Peak consumption rate is
maintained over a small
temp range.
 Consumption rate
decreases rapidly as temp
increases.
 Lethal temperature finally
achieved.
Chemical Varibles: Dissolved Oxygen (DO)/
Sources
 Major producer of D.O. in ponds is primary productivity
(up to 80%), diffusion is low (<3%).
 Incomingwater can often be deficient depending
upon source water conditions.
 Majorconsumers: primary productivity, aquatic
species (density dependent), COD.
 Diel fluctuation
 Indirect relationships (algae, secchi)
Chemical Varibles: Dissolved Oxygen (DO)
Oxygen budget
Input O2 (kg/ha) % of total
Photosynthesis 4,130 76.9
Inflowing water 94 1.7
Aeration 99 1.8
Diffusion 1,050 19.6
Total 5,373 100.0
Output
Overflow, drainage 32 0.6
Phyto respiration 3,090 57.5
Benthic respiration 1,040 19.4
Fish/shrimp resp. 1,210 22.5
Total 5,372 100.0
Chemical Varibles: Dissolved Oxygen (DO)

 Diel Oxygen Fluctuation

 Typical
pattern = oxygen
max during late afternoon.
 Difference in surface vs.
benthic for stratified
ponds.
 Dryseason = faster heating
at surface and less
variation.
Chemical Varibles: Dissolved Oxygen (DO)

Influence of
Sunlight on
Photosynthesis/O2
Production
Chemical Varibles: Dissolved Oxygen (DO)

Photorespiration:
predictable
Chemical Varibles: Dissolved Oxygen (DO)

Photorespiration:
predictable
Chemical Varibles: Dissolved Oxygen (DO)/
Measurement
 Collection of Sample
 Samples are collected in a narrow necked glass
sloppened bottle
 Avoid the formation of air bubble below the stopper
 Determination of DO
 Nitrites, sulphides, sulphites, ferrous compounds and
organic matter etc. are oxidized
 1 ml KMnO4 and 0.7 ml of H2SO4
 Shake well and allowed to stand for 20 minutes
Chemical Varibles: Dissolved Oxygen (DO)/
Measurement
 Collection of Sample
 Samples are collected in a narrow necked glass
sloppened bottle
 Avoid the formation of air bubble below the stopper
 Determination of DO
 Nitrites, sulphides, sulphites, ferrous compounds and
organic matter etc. are oxidized
 1 ml KMnO4 and 0.7 ml of H2SO4
 Shake well and allowed to stand for 20 minutes
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.
Chemical Variables: Total Alkalinity
 Thus, a total alkalinity determination of 200 mg/L would indicate good
buffering capacity of a water source.
 Natural freshwater alkalinity varies between 5 mg/L (soft water) to over
500 mg/L (hard water).
 Natural seawater is around 115-120 mg/L.
 Seldom see pH problems in natural seawater.
 Water having alkalinity reading of less than 30 mg/L are problematic.
Chemical Variables: Total Alkalinity
Total Alkalinity level can be associated with several potential
problems in aquaculture:
 < 50 mg/L: copper compounds are more toxic, avoid their use
as algicides.
 Natural waters with less than 40 mg/L alkalinity as CaCO3 have
limited. biofiltration capacity, pH independent
 Low alkalinity = low CO2 --> low nat prod.
 Low alkalinity = high pH.
Chemical Variables: Total Hardness
 Total Hardness: total concentration of metal ions expressed in terms
of mg/L of equivalent 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.
Chemical Variables: pH
 pH: the level or intensity of a substance’s 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
Chemical Variables: pH
 At acidic pH levels, the quantity of H+ predominates.
 Acidic pH = pH < 7, basic = pH >7
 Mostnatural 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: pH
 This causes blood CO2 levels to increase, lowering blood
pH.
 Withlower 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.
Chemical Variables: pH

CO2 Level Affects

Hemoglobin
Saturation
Chemical Variables: carbon dioxide
 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?
Chemical Variables: carbon dioxide

The Effect of pH on
Carbonate
Buffering
Chemical Variables: carbon 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
Chemical Variables: 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.
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.
 Alkalinityin 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.
Chemical Variables: Total Alkalinity
 Thus,a total alkalinity determination of 200 mg/L
would indicate good buffering capacity of a water
source.
 Natural freshwater alkalinity varies between 5 mg/L
(soft water) to over 500 mg/L (hard water).
 Natural seawater is around 115-120 mg/L.
 Seldom see pH problems in natural seawater.
 Water having alkalinity reading of less than 30 mg/L
are problematic.
Total Alkalinity
Total Alkalinity level can be associated with several
potential problems in aquaculture:
<50 mg/L: copper compounds are more toxic,
avoid their use as algicides.
 Natural
waters with less than 40 mg/L alkalinity as
CaCO3 have limited. biofiltration capacity, pH
independent
 Low alkalinity = low CO2 --> low nat prod.
 Low alkalinity = high 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.
 Calciumis used for bone and exoskeleton formation
and absorbed across gills.
 Soft water = molt problems, bone deformities.