Recirculating Aquaculture - Cap 2
Recirculating Aquaculture - Cap 2
Recirculating Aquaculture - Cap 2
39
40 Chapter 2 Water Quality Phys ical Properties 41
result provided a lesson learned the hard way about why it is important to molasses o r motor oil, flow very slowly when subject t o a shear stress.
understand the interrelationships of these parameters, and to routinely Absolute viscosity is measured in centipoises, and water at 20°C has a
monitor as many critical water quality parameters as possible and when value of 1 .0 centipoise, compared to air, which has a value of 0.17
adjustments are needed, to make them carefully and slowly. centipoise, at this temperature. The absolute viscosity divided by the
The relationship between water quality parameters and their effect on liquid density is the given the name kinematic viscosity. Table 2.1 shows
fish growth rate and health is complicated. For example, fish lack the the variation of density, absolute viscosity, and kinematic viscosity of
means to control their body temperature and maintain it independent of water at a range of temperatures. Viscosity increases as temperature
the environment. Environmental temperature changes affect the fishes' decreases. Thus, pumping costs will increase slightly as water
rate of biochemical reactions, which leads to different metabolic and temperature decreases because viscosity and density both increase.
oxygen consumption rates. At the lower ranges of the species tolerable Vapor pressure is the pressure exerted by the gaseous phase of a
temperature range, these rates decrease. As water temperatures increase, material when in equilibrium with its solid or liquid phase. Another way
fish become more active and consume more dissolved oxygen, while of expressing vapor pressure is the pressure at which a liquid just begins
simultaneously producing more carbon dioxide and other excretory to boil and change to a vapor (Lawson, 1995). Vapor pressure of pure
products, such as ammonia. These increasing rates of consumption of water is a function of temperature and increases with an increase in
necessaty elements and production of dettimental elements can have a temperature, Table 2.1. The addition of salt to water lowers its vapor
direct effect on overall fish health and survival if these parameters are pressure. In a closed pipe, water may change phase from a liquid to a
allowed to exceed nominal values. If not coJTected, the fish will become vapor because of a reduction in pressure, even though the temperature
stressed to some degree. Even low levels of stress can have adverse long remains unchanged. This can occur on the suction side of pipe, where
term consequences in the form of reduced growth rates or mortality due vapor bubbles form in local regions of very low pressure and then
to opportunistic organisms that take advantage of the stressed fish. collapse when they move into regions of higher pressure downstream.
This process is called cavitation. When a pump is cavitating, the
collapsing bubbles contain a great deal of energy and can cause
2.1 PHYSICAL PROPERTIES considerable damage to pump impe!Jers and pipes.
Several physical properties of water are important for the Table 2.1 Physical Properties of Water
understanding of some of the engineering concepts that follow. Water
has several very unique properties that make life on the planet possible. Kinematic Viscosity Vapor Pressure
Formulae for generating water physical properties (T is in °C): corresponding costs involved in the treatment of large discharge flow
streams.
Density (kg/m3) = 999.842594+6.793952£-2-T There are three categories of reuse systems: serial-reuse systems,
-9.095290E-3·T2 + 1 .001 685E-4-T3 - partial-reuse systems, and fully recirculating systems. Partial-reuse
1 . 1 20083E-6·l"+6.536336E-9-T5 (2.1) systems reuse a greater percentage of total system volume than do serial
reuse systems, and the fully recirculating systems reuse a greater
Vapor Pressure (mm Hg) 4.7603 e0·064H
=
(2.2) percentage of total system volume than do the pa11ial-reuse systems. The
degree of water reuse affects the depletion/accumulation rate of
Kinematic Viscosity (m2/s 1 0-6) - -9.9653E-6 -r important water quality parameters. The greater the reuse rate, the more
+0.00 l l 43T2-0.05807T + 1.7851 (2.3)
conditioning the reused water must have in order to restore the water
quality to target parameters. Typically, the most important and first
encountered limiting factor that governs the density of fish reared in a
2.2 WATER QUANTITY REQUIREMENTS system is the concentration of dissolved oxygen. The next most
important factors are the amounts of unionized ammonia and dissolved
During the initial site selection process, one of the most critical carbon dioxide levels. These two parameters are interconnected. This is
fact�r� �o consi�er is the availability of an adequate water supply for both due to the direct effect that dissolved carbon dioxide has on pH and the
_
the 111Jttal facli1ty and any planned (or imagined) expansion. When it relationship of pH to the toxicity of ammonia-nitrogen. As the dissolved
�omes to the availability of water, too much is definitely better than too carbon dioxide levels decrease, the pH increases, which in turn increases
little. After all, one is constmcting an AQUAculture facility. The amount the toxicity of the total ammonia-nitrogen in the system. For example, if
of water needed V.:ill depend on several factors such as species, density, salmonids are the species being grown, the maximum upper safe limit for
�an�g�ment practices, production technology, and the degree of risk one chronic exposure to carbon dioxide is from <9 to 30 mg/L, and for
IS willmg to accept. At a minimu
m, sufficient quantities of water are unionized ammonia-nitrogen <0.0125 to 0.03 mg/L. The chosen reuse
needed to routinely fill production tanks within a reasonable time (24-48 system must be able to sustain the necessary levels of dissolved oxygen
hrs), provide for routine and emergency flushing of tanks filter while also keeping the amounts of dissolved carbon dioxide, unionized
backwashing, facility wash down and clean-up, and d�mestic ammonia, and the pH below their respective limiting levels.
_
reqUirem ents. A good rule of thumb is to have sufficient water available Serial-reuse systems have been used extensively in trout and
to provide a 100% water exchange of total system volume per day salmonid raceway production systems, where the limiting water quality
(Timmons, 2000). Thus for a total system volume of 379 m3 ( 1 00,000 factor is usually the dissolved oxygen concentration between raceway
gallons), a water supply is required that is able to provide 379 m3 per day sections. By adding oxygen, the water can be used over again in the next
or 0.26 m3/mm (70 gpm). This may be reduced some for a warm water section of the raceway, until ultimately the accumulated ammonia levels
species. become too high. This simple concept has significantly increased
Beyond the _ minimum exchange volume, the additional quantity of raceway production, but at a higher system cost due to the requirements
new water rcquued for any given system is directly dependent on the for more sophisticated oxygenation systems and monitoring systems.
degree of reuse or recycling of the "old" water that is already available in Economic risk is also higher, because there are more fish in the raceway
the system. There are numerous reasons to reuse the supply water as that arc subject to a catastrophic event.
much as possible, besides the obvious decrease in water demand and Partial-reuse systems are an alternative culture system that can
reduced discharge water that must be treated. These include the reduction sustain high production densities on less than 20% of the total flow that
of water heating or cooling requirements, which arc major factors in the would be required tu grow the same quantity of fish in a serial-reuse
econ_omics of many warm-water species production systems. system (Summerfelt, et al., 2000). Some partial-reuse systems separate
AddJtJon _ ally, and becomin
g increasingly important, recycling of system the solid wastes from the main water recirculation loop by using a dual
waters results in the reduction in wastewater discharge and the drain system. In this system, the circular production tank is used as a
"swirl" separator to concentrate the solids into the center drain. From
44 Chapter 2 Water Quality Water Sources 45
there, they arc removed with a relatively small discharge flow stream
100
( 1 5 20% of the quantity of water in the tank per day). The majority of
the water flow leaving the tank, i.e., the remaining 80-85%, is
discharged from the tank through a fish-excluding port located
tank sidewalL This flow stream is 0.
_,
oxygenation system. The ammonia levels are controlled by dilution with 10 400 m t/L
c
0
controlling the system pH. The key operating water quality parameter in �
...
<T
this type of system is the amount of dissolved carbon dioxide. Adjusting I0 0 m g/L
the water will have a low pH, and thus the corresponding maximum total
·"I
ammonia-nitrogen level will also be well below the level at which it
100.0
would become criticaL
The nomograph in Fig. 2.1 provides an estimate of the maximum
total ammonia-nitrogen that can be allowed to accumulate in a partial 30.0
_, 20.0
reuse system, depending upon the water's alkalinity and assumed ;a,
E
maximum limits on the concentrations of dissolved carbon dioxide and I 0.0
;;
«>
unionized ammonia (Summerfelt et aL 2000). Thus setting the maximum g
·;:
limits on the concentrations of dissolved carbon dioxide and unionized .� 3.0
g 2.0 EquiL N H ,
ammonia, at a given alkalinity, will set the minimum operating pH and E
0.025 mg/L
the maximum allowable total ammonia-nitrogen. � 1.0
-;;;
0 0 . 0 1 2 5 mg/L
<-
2.3 WATER SOURCES 0.3
0.2
One of the most important requirements for a successful aquaculture
0.1
facility site is a high quality water source, with sufficient capacity to
6.0 6.5 7.0 7.5 8.0
provide for initial needs and contemplated future expansions. Thus, when
pll
choosing an aquaculture site, the water supply must be thoroughly
investigated and quantified in terms of both quality and quantity. Figure 2.1 Dependence of dissolved carbon dioxide concentrations on pH and
Aquaculture is unlike other agriculture activities, in that it requires a alkalinity (top graph), and unionized ammonia concentrations and total
continuous supply of high quality water. Most wells operate only ammonia-nitrogen (bottom graph), according to acid-base equilibrium at 15°C.
periodically, so a traditional well pump test is usually conducted for only Dashed lines indicate how setting a maximum limit of 20 mg/L on the
a short time, to measure the well's ability to deliver a certain quantity of concentration of dissolved carbon diO)(ide ( 1) and of 0.0125 mg!L on unionized
water within a cettain time. However, under normal aquaculture ammonia nitrogen (3), at an alkalinity of I 00 mg/L (2), will set the minimum
operations, the well is pumped continuously. The result can be that the operating pH (about 7.06) and the maximum allowable TAN (4) (about 5.0
mg!L), from Summerfelt et al. 2000.
actual productivity of the well is significantly less than indicated by the
short duration test This will result in serious difficulties down the road.
46 Chapter 2 Water Quality
Chapter 2 Water Quality 47
are exposed to constant concentrations of toxic substances, while Table 2.2a Water Quality Criteria for Aquaculture
maintaining other water quality parameter$ within an acceptable range.
Parameter Concentration (mg!L)
The extrapolation of these types of experiments to the entire production
Alkalinity (as CaCO,) 50-300
cycle and to combinations of environmental parameters (for example, Aluminum (AI) <0.01
high total ammonia, and carbon dioxide in combination with Ammonia (NH3-N unionized) <0.0125 (Sahnonids)
Ammonia (TAN) Cool-water fish <1.0
supersaturated dissolved oxygen) i s difficult if not impossible (Colt,
Ammonia (TAN) Warm-water fish <3.0
2006). These types of exposures seldom occur in real systems. A real Arsenic (As) <0.05
world evaluation of ammonia toxicity might test the impact of diel Barium (Ba) <5
varying ammonia concentration on the growth of 300-400 g tilapia under Calcium (Ca) 4-160
Carbon Dioxide (C02)
high carbon dioxide levels when DO is maintained at 70% of saturation, Tolerant Species (tilapia) <60
and alkalinity is low. Sensitive Species (salmonids) <20
The water quality criteria for the design of culture systems depend Chlorine (Cl) <0.003
Hardness, Total (as CaCOJ) >lOO
strongly on the objectives of the project, species and life stage grown.
Hydrogen cyanide (HCN) <0.005
The impact of water quality on growth is probably the most important Hydrogen sulfide (H2S) <0.002
consideration. Other impacts include fin quality and appearance which i s Iron(Fe) <0.1 5
Lead (Pb) <0.02
important for species sold in the ' l ive-market'; tissue quality such as
Magpesium (Mg) <15
texture, taste and odor and finally trace contaminates in the tissue such as Manganese (Mn) <0.01
methymercmy, PCT, DDT or dioxins (Colt, 2006). Development of Mercury (Hg) <0.02
species or system specific water quality criteria is time consuming and Nitrogen (N2) <110% total gas pressure
<103% as nitrogen gas
expensive (Colt, 2006). A summary of important water quality
Nitrite (N02) <I, 0.1 in soft water
parameters i s presented in Table 2.2 and provides ve1y general Nitrate (NOJ) 0-400 or higher
recommendations of water quality criteria for each parameter. Colt Nickel (Ni) <0.1
Oxygen Dissolved (DO) >5
(see Chapter 4 for more detail)
(2006) provides additional details, especially regarding nitrite
> 90 mm Hg partial pressure
concentrations. Ozone (0,) <0.005
Several other water quality parameters are currently being carefully PCBs <0.002
pH 65-8.5
reviewed due to the uncertainty as to their impact on production. The
Phosphorous (P) 0.01-3.0
effect of high levels of fine solids and organic compounds is unknown at Potassium (K) <5
this time, but has been implicated i n disease outbreaks (Bullock, et al., Salinity depends on salt or fresh species
1994). The leaching of surface-active compounds from uneaten feed and Selenium (Se) <0.01
Silver (Ag) <0.003
fecal matter and the resulting depression of surface tension may be an
Sodium (Na) <75
impottant design consideration (Colt, 2006). In limited exchange Sulfate (SO.) <50
systems, there is a potential to build-up toxic concentrations of some TGP (total gas pressure) <I 05% (species dependent)
heavy metals, such as cadmium, copper and zinc from the corrosion of Sulfur (S) <I
Toal
t dissolved solids (TDS) <400 (site specific and species
pipes and fittings and from vitamin premix. The toxicity of heavy metals specific; use as rough guideln i e)
depends strongly on water chemistry. Finally, there is limited data on the Toal
t suspended solids (TSS) 1 0 to 80 (species dependent)
impact of pheromones, endocrine-disrupting chemicals (EDCs), and Uranium (U) <0.1
Vanadium (V) <0.1
chemicals leached from paints, PVC components, and liners. These
Source� Meade., 1985� Pipe.t et aL 19&4 Lawson, 1995
chemicals can exert profound and adverse effects on aquatic animals by
interfering with the endocrine systems and potentially resulting in
reduced fertility (Colt, 2006) and lower growth rates. The environmental
chemistry of different EDCs is complex and the analysis is costly.
l Water Sources 51
50 Chapter 2 Water Quality
Table 2.2b HeavyMetal Water Quality Criteria Table 2.3 Dissolved Oxygen (mg 02 per Liter, ppm) at Saturation in
Seawatcr
Freshw ater Freshwater, Brackish Water, and Seawater at Different
Metal
�
7
5. 0*
0�� �--
--7
10
�0--
�. --
--�
10
� .--
--�
�
.--
� ---
Temperatures
(pgL)
Copper 35 9 1.3 0.18 3.1 Temp Salinity, parts per thousand
Zinc 460 120 17 2.4 81 5 10 15 20 25 30 35 40
0
Cadmium 0.75 0.25 0.049 0.01 8.8
14.112 1 3 .638 13.180 12.737 12.309 1 1 .896 1 1 .497 11.111
*Hardness (mg/L as CaC03) 0 14.602
13.725 13.268 12.825 12.398 1 1.984 1 1 .585 1 1. 1 9 8 10.825
Source: Colt, 2006 1 14.198
13.356 12.914 12.487 12.073 1 1 .674 I 1.287 10.913 10.552
2 13.813
13.004 12.576 12.163 1 1 .763 1 1 .376 1 1.003 10.641 10.291
3 13.445
12.667 12.253 1 1 .853 1 1 .467 1 1 . 092 10.730 10.380 10.042
4 13.094
10.131 9.802
2.5 WATER QUALITY PARAMETERS
5 12.757 12.344 1 1.944 1 1 .557 1 1 . 183 10.820 10.470
12.036 1 1 .648 1 1.274 10.911 10.560 10.220 9.892 9.573
6 12.436
1 1 .002 10.651 10.311 9.981 9.662 9.354
DISSOLVED OXYGEN
7 12.127 1 1 .740 1 1.365
1 1 .457 1 1 .093 10.742 10.401 10.071 9.752 9.443 9.143
8 1 1 .832
9.532 9.232 8.941
Of all the water quality parameters, dissolved oxygen is the most
9 1 1 .549 11.185 10.833 10.492 10.162 9.842
10.925 10.583 10.252 9.932 9.621 9.321 9.029 8.747
1 1 .277
important and most critical parameter, requiring continuous monitoring
10
10.674 10.343 10.022 9.711 9.4!0 9.118 8.835 8.561
1 1 1 1 .016
in intensive production systems. Nature played a cruel joke on
10.434 10.113 9.80.1 9.499 9.207 8.923 8.648 8.381
aquaculture when she decided that the saturation concentration of 12 10.766
10.203 9.891 9.589 9.295 9.011 8.735 8.468 8.209
dissolved oxygen would be higher at low temperature and lower at high 13 10.525
9.981 9.678 9.384 9 099 8.823 8.555 8.295 8.043
14 10 294
9.473 9.188 8.9 1 1 8.642 8.381 8.129 7.883
temperatures. This condition is exactly the opposite of what fish require
15 10.072 9.768
9.562 9.276 8.998 8.729 8.468 8.214 7.968 7.730
16 9.858
for basic metabolism and food conversion, which is higher at high
9.364 9.086 8.816' 8.554 8 300 8.053 7.814 7.581
temperatures and lower at low temperatures. Although the air we breathe 17 9.651
9.174 8.903 8.640 8.385 8.138 7.898 7.664 7.438
contains 2 1 % oxygen, oxygen is only slightly soluble in water. As a 18 9.453
9.265 8.990 8.726 8.471 2.222 7.982 7.748 7.521 7.300
19
8.812 8.556 8.307 8.065 7.831 7.603 7.382 7.167
result, aquatic species must spend a great deal of energy to remove the
20 9.077
8.641 8.392 8.149 7.914 7.685 7.463 7.248 7.038
21 8.898
dissolved oxygen from water, as compared to the energy that land
8.726 8.476 8.233 7.997 7.767 7.545 7.328 7.118 6.914
dwelling species expend to obtain oxygen from the air. In addition, the 22
8.560 8.316 8.080 7.849 7.626 7.409 7.198 6.993 6.794
23
6.677
solubility of oxygen decreases as salinity increase. Both barometric
8.162 7.931 7.707 7.489 7.277 7.072 6.872
24 8.400
7.788 7.569 7.357 7.150 6.950 6.754 6.565
pressure and altitude also directly affect oxygen concentration. Table 2.3
25 8.244 8.013
8.094 7.868 7.649 7.436 7.229 7.027 6.831 6.641 6.456
26
lists the saturation oxygen concentration in water as a function of salinity
7.729 7.515 7.307 7.105 6.908 6.717 6.531 6.350
and temperature. 27 7.949
7.808 7.593 7.385 7.182 6.984 6.792 6.606 6.424 6.248
It ls difficult to specify critical dissolved oxygen concentrations, 28
7.671 7.462 7.259 7.060 6.868 6.680 6.498 6.321 6.148
29
6.755 6.572 6.394 6.221 6.052
because the response to low dissolved oxygen is not life-or-death, but a
30 7.539 7.335 7.136 6.943
7.212 7.018 6.829 6.645 6.466 6.293 6.123 5.959
31 7.411
continuum of physiological effects. ln addition, these effects are
7.092 6.903 6.718 6.539 6.364 6.194 6.029 5.868
influenced by the exposure time, the size, and health of the fish, water 32 7.287
6.976 6.791 6.611 6.435 6.265 6.099 5.937 5.779
temperature, concentration of carbon dioxide, and other environmental 33 7.166
7.049 6.863 6.682 6.506 6.335 6.168 6.006 5.848 5.694
34
6.074 5.915 5.761 5.610
conditions. In general, though, warm water fish feed best, grow fastest,
35 6.935 6.753 6.577 6.405 6 237
6.647 6.474 6.306 6.142 5 983 5.828 5.676 5.529
36 6.824
and are healthiest when dissolved oxygen concentrations are above about
For sahnonids, as a group, the rearing unit effluent should contain other metabolic processes ensure that the law of diminishing returns
from 6.0 to 8.0 mg/L dissolved oxygen (DO). For catfish and tilapia, applies. In addition, at higher than optimum temperatures, the fish food
allowable minimum levels are much lower than for salmonids, e.g., 2 or conversion ratios are lower. Further temperature increases beyond
3 mg/L, while it is certainly recommended to stay much closer to 5 or 6 optimum are of no benefit, and may in fact approach lethal levels. Thus
mg/L. This variation in what the allowable minimums are has to do with to insure maximum growth and minimize stress, system temperatures
the fact that partial oxygen pressure (p02) appears to be a more valid way need to be maintained as close as possible to optimum value. Optimum
to determine the lower limits. A p02 of 90 mm Hg seems to be a temperature range for several representative species is presented in Table
reasonable target for salmonids (Downey and Klontz, 1 9 8 1 ). The 2.4.
atmosphere contains 2 1 % oxygen, and at standard pressure of 760 mm
Hg at 20°C, this represents a p02 of 0.21 • (760-1 7 . 54)" or 155.9 mm Table 2.4 Optimum Temperature Ranges (0C) for Representative
Hg. and corresponds to a dissolved oxygen saturation of 9.1 mg/L. Aquaculture Species
Temp. Source
Therefore, 90 mm Hg corresponds to 5.2 mg/L DO. If the temperature is
Species Range
5°C, p02 corresponds to 0.21 (760 - 6.54) or 158.2 mm Hg and
12- 1 4°
•
temperature range, growth rates increase as the water temperature proteins, nucleic acids, adenosine phosphates, pyridine nucleotides, and
pigments. However, nitrogen is required in relatively small quantities,
increases, until the optimum temperature is reached. Above the optimum
temperature, the increased energy requirements for food conversion and and physiological needs are easily satisfied. Excess quantities then
become nitrogenous wastes, and removal is necessary. The fish create
and expel various nitrogenous waste products through gill diffusion, gill
• 17.54 mm Hg is the vapor pressure of water at 20°C
J
54 Chapter 2 Water Quality Water Sources 55
cation exchange, and urine and feces excretion. In addition to the For example, given a TAN = 5.0 mg/L in fresh water at 20°C and a
a�monia, urea, uric acid, and amino acid excreted by the fish, pH of 7.0, the concentration of unionized ammonia is only 0.020 mg/L,
mtrogenous wastes accumulate from the organic debris of dead and which has a negligible impact on most fish. However, at a pH of9.0, the
dying organisms, uneaten feed, and from nitrogen gas in the atmosphere. unionized ammonia increases to 1 .43 mg/L, killing most species of fish
�ecot�posing these nitrogenous compounds is particularly important in in hours. The fraction of unionized ammonia at different temperatures
mtenstve RAS because of the toxicity of ammonia, nitrite, and to some and pH are included in the Appendix.
.
extent, nitrate. Ammonia appears to have a direct effect on the growth �f aqua�1c
Ammonia, nitrite, and nitrate are all highly soluble in water. animals. Unionized ammonia is toxic to fish at low concentrations, w1th
Ammonia exists in two forms: unionized NH3' and ionized Nil/ 96-hour LC50's varying widely by species from as low as 0.08 mg/L NIIJ
(ammonium). The relative concentration of the two forms of ammonia is N for pink salmon to 2.2 mg/L NH3-N for common carp. In general,
primarily a function of water pH, salinity, and temperature. The sum of warm-water fish are more tolerant to ammonia toxicity than cold-water
the tvvo (NH/+ NHJ) is called total ammonia nitrogen or simply fish, and freshwater fish are more tolerant than saltwater fish. In general,
ammonia. It is common in chemistry to express inorganic nitrogen for commercial production, unionized ammonia concentrations should be
compo�nds in terms of the nitrogen they contain, i.e., NH/-N (ionized held below 0.05 mg/L and TAN concentrations below 1.0 mg/L for long
_
ammonta nttrogen), NH3-N (unionized ammonia nitrogen), N02"-N tem1 exposure. Table 2.5 summarizes the effects of temperature and pii
(nitrite nitrogen) andN03·-N (nitrate nitrogen). This allows for easier on the percentage of free ammonia in freshwater.
computation of total ammonia-nitrogen (TAN = NH/-N + NH3-N) and
_ Table 2.5 Percentage of Free Ammonia (as
easy conversiOn between the various stages of nitrification. NH3) in Freshwater at Varying
(!l l and Water TcmEerature,�Lawson,19952
DEFINITIONS 1o·c IS"C 2o·c 2s·c 3o·c
pH (86.F2
�5o·F) (59. F
2 (68.F2 (77.F2
•
NH3-N = unionized ammonia nitrogen (ammonia) 0.1
6.0 0.1
•
NH4+_N = ionized ammonia nitrogen (ammonium)
6.5 0.1 0.1 0.1 0.2 0. 3
•
TAN = NH/-N + NH3-N
• 7.0 0.2 0.3 0.4 0.6 0.8
N02·-N = nitrite nitrogen
• 7.5 0.6 0.9 1.2 1.8 2.5
N03·-N = nitrate nitrogen
8.0 1.8 2.7 3.8 5.4 7.5
Unionized ammonia (NH3-N) is the most toxic form of ammonia 8.5 5.6 8.0 1 1 .2 15.3 20.3
becau�e of its ability to move across cell membranes, so the toxicity of 9.0 15.7 2 1 .5 28.4 36.3 44.6
TAN IS dependent on the percentage present in the unionized form. An 9.5 37.1 46. 4 55.7 64.3 71.8
in�rease in pH, temperature, or salinity increases the proportion of the 10.0 65.1 73. 3 79.9 85.1 89.0
umo111zed form of ammonia nitrogen. The concentration of NH3-N can
b e computed knowing the pH from the following equation:
Nitrite is the ionized fonn of the relatively strong acid, nitrous acid
and is the intermediate product in the process of nitrification of ammonia
TAN
NHJ - N = ------
�+ lO(pKa-piiJ)
to nitrate. Although nitrite is converted to nitrate relatively quickly by
(2.4)
ozone or by the nitrifying bacteria in a properly balanced biofilter, it is a
problem in reci..tculating systems because it can build u� easily �
if he
second bacterial driven stage of the nitrification process ts not workmg
where TAN is the measured concentration of total ammonia nitrogen properly.Therefore, it is an important water qualityya�amet�r to monit�r
_
(mg/L); pKa, the acidity constant for the reaction (9.40 in fresh water at and correct if acceptable limits are exceeded. Nttnte JS tox1c because 1t
20 °C); pH, the measured pH of the solution; NH3- N, computed affects the blood hemoglobin's ability to carry oxygen. When nitrite
concentration in (mg/L). enters the bloodstream, it oxidizes the iron in the hemoglobin molecule
56 Chapter 2 Water Quality Water Sources 57
from the ferrous state to the ferric state. TI1e resulting product is called ALKALINITY!HARDNESS
methemoglobin, which has a characteristic brown color, hence the
In broad tcn11S, alkalinity is a measw-e of the pH-buffering capacity
common name "brown-blood disease". The amount of nitrite entering the
or the acid-neutralizing capacity of water. In chemical terms, alkalinity is
blood depends on the ratio of nitrite to chloride in the water, in that
defined as the total amount of titratable bases in water expressed as mg!L
increased levels of chloride reduce the amount of nitrite absorption.
equivalent calcium carbonate (CaC03). Sometimes alkalinity is
Chloride levels can be increased by adding ordinary salt (sodium
chloride) or calcium chloride. At least a 20 I : ratio of chloride to nilritc
expressed as milliequivalentslliter, where 1 meq/L equals 50 mg/L as
CaC03. The principle ions that contribute to alkalinity are carbonate
X:itro_gen (Cl: NOrN) is recommended for channel catfish in ponds,
(C03 ") and bicarbonate (Hcon. Table 2.6 provides a list of commonly
tllapta, and rainbow trout.
used alkalinity supplements, their relative solubility, and their
Nitrate is the end-product of nitrification and is the least toxic of the
equivalents basis (see also Chapter 7 for discussion of nitrification and
nitrogen compounds, with a 96-h LC50 value usually exceeding 1000 mg
alkalinity consumption). See the appendix for hardness conversions to a
NOrN IL. In recirculation systems, nitrate levels are usually controlled
variety of units.
by dail� water exchanges. In systems with low water exchange or high
hydrauhc retention times, denitrification has become increasingly
Table 2.6 Alkalinity Supplement Properties (Bisogni and Timmons, 1994)
important (see Chapter 9).
Chemica l Equivalent Rate of
PH Formu la Common Name(s) Wt. (gm/eq.) Solubility solubilization
TI1e pH value expresses the intensity of the acidic or basic NaOH sodium hydroxide 40 high rapid
characteristic of water. In simplified chemical terms, pH is the negative rapid
_ Na2C03 sodium carbonate 53 high
loganthm of the hydrogen ion concentration. The pH scale ranges from 0 soda ash
to 14, with a pH of7.0 corresponding to the neutral point. Values ofpH NaHC03 sodium 83 high rapid
below 7.0 are acidic (the 1-r ion predominates), and above 7.0, values are bicarbonate
+
basic or alkaline (the OH ion predominates). The pH of most baking soda
groundwater's and surface waters is buffered by the bicarbonate CaC03 calcium carbonate 50 moderate moderate
carbonate system and has pJI values between 5 and 9. Exceptions to this cal cite
CaO slaked lime 28 high moderate
are groundwater with high concentrations of dissolved carbon dioxide
�nd water draining from some mines (acid mine drainage, AMD). AMD Ca(OH)2 calcium hydroX-ide. 37 high moderate
IS the result of the oxidation of mineral sulfides, which becomes sulfuric hydrated lime
acid. Seawater is buffered by the bicarbonate-borate system and has a CaMg(C03)2 dolomite 46 moderate slow
relatively stable pH between 8.0 and 8.5. The optimum pH for the
MgC03 magnesium 42 moderate slow
growth and health of most freshwater aquatic animals is in the range of
carbonate
6 . 5 to 9.0.
magnesite
Exposure to extreme pH can be stressful or lethal but it is the
Mg(OH)2 magnesium 29 moderate slow
�
indirect effects resulting from the interactions of pH with ther variables hydroxide
that �r� more imp?��t in aquaculture. pH controls a wide variety of brucite
solubthty and eqmhbna reactions, the most important of which is the Note: Na compounds are highly soluble in water while Mg compounds have poor
relationship between the unionized and the ionized form of ammonia and solubility. Ca compounds a.re intermediate. Mg compounds tend to dissolve very
nitrite. pH also affects the toxicity of hydrogen sulfide and metals such slowly, so may have application in situations requiring a long-term application. Na
compounds may prove to be the most expensive.
as copper, cadmium, zinc and aluminum.
Based on lOO% pure compound. To calculate (or impurities, divide the tabulated value by
the pure fraction ({100%-impurities %}/100 gives pure fraction) to get the true
value.
58 Chapter 2 Water Quality Water Sources 59
In practical terms, alkalinity is measured by titration with sulfuric or water solubility and rapidly dissolves in water at ambient temperature. A
hydrochloric acid to the methyl orange endpoint (pH of 4.5). Alkalinity general rule of thumb is that for evety pound of feed, approximately 0.25
of freshwater ranges from less than 5 mg/L in soft water to over 500 lbs ( 1 1 3 g) of sodium bicarbonate should be added to the water. Carbon
mg/L, and is determined by the geology of the aquifer or watershed. The dioxide concentrations are routinely controlled through degasification
alkalinity of seawater is about 120 mg/L CaC03. Required alkalinity systems, such as counter-flow gas stripping towers.
concentrations are directly linked to system pH and carbon dioxide Hardness is the term used to describe the ability of water to
concentrations. Maintaining carbon dioxide concentrations at less than precipitate soap, the harder the water, the greater the amount of soap that
1 5 mg/L and pH between 7.0 and 7.4 requires an alkalinity concentration must be added to a given volume of water to get the same cleaning
less than 70 (high pH condition) to
190 mg/L CaC03 (low pH condition). action. In chemical terms, hardness is defined as the total concentration
The relationship between pH, alkalinity, and C02 concentrations i s of primarily calcium (Ca2+) and magnesium (Mg2+), iron, and manganese
shown i n Fig. 2.2. in terms of mg/L equivalent calcium carbonate (CaC03). In practical
terms, hardness is measured by chemical titration. The total hardness of
100.0 natural waters ranges from less than 5 to over 1 0,000 mg/L CaC03.
1\\ \\
Waters have traditionally been classified as soft (0-75 mg/L), moderately
90.0
--alk = 25 mg/L hard (75-150 mg/L), hard (1 50-300 mg/L), or very hard (> 300 mg/L).
80.0 1- Hardness is often confused with alkalinity, probability because both
--alk 50 mg/L
are commonly defined in terms of mg/L CaC03. In fact, if the alkalinity
\
70.0
=
1-
\ 100 mg!L
of the water originates from limestone, the concentrations of hardness
\ \
60.0
--alk
...I
=
f.--- and alkalinity can be similar if not identical. Conversely, many coastal
0,
1\ \ \
50.0 plain area groundwaters have high alkalinity and very low hardness
E
concentrations. Aquifers in regions of basalt and granite often have
\. "\ �
N 40.0
0 waters of low total hardness and. low alkalinity, because of the relative
(.)
'....' '
30.0 low solubility of these minerals. If this low hardness and low alkalinity
water i s used for aquaculture, the water must be "hardened" by adding
�� �
20.0
dissolved calcium to support newly fertilized freshwater fish eggs and for
.._,
10.0 calcification of larval skeletal structures. Calcium and magnesium also
-....._.__, � decrease the toxicity of dissolved metals. Recommendations for total
0.0
��
hardness range-from 20 to 300 mg/L.
6.00 6.50 7.00 7.50 8.00
pH
CARBON DIOXIDE AND THE CARBONATE CYCLE
Figure 2.2 The relationship between pH, alkalinity, and C02 concentrations
when alkalinity is 25, 50, & 100 mg/L at zero salinity and 20 °C (Note Carbon dioxide is highly soluble in water, but concentrations i n pure
C02 concentration is proportional to alkalinity). water are low (0.54 mg/L at 20°C), due to its low concentration in the
atmosphere (about 0.035% by volume). Most of the carbon dioxide in an
In recent years, as aquaculture system stocking density and hydraulic aquaculture water column is produced by animal respiration and the
retention time has increased, the relationship between pH and alkalinity decomposition of organic matter. The concentration of carbon dioxide i n
has become a significant issue. This relationship requires careful groundwater can range from 0 to 100 mg/L, depending o n the biological
monitoring and adjustment of both alkalinity and carbon dioxide levels to activity in the aquifer recharge zone_ The concentration of dissolved
maintain optimum pH for both the aquatic species being grown and the carbon dioxide in surface waters depends on the rate of respiration,
biofilters. Alkalinity is easily adjusted through the addition of sodium photosynthesis, and gas exchange with the atmosphere.
bicarbonate (NaHC03), common baking soda. Other materials can be Exposure to high carbon dioxide concentrations reduces respiration
used, but sodium bicarbonate is commercially available in 23 to 45 kg efficiency and decreases the tolerance to low dissolved oxygen
(50 to 100 lb) bags, safe, inexpensive, and easy to apply. It has very high concentrations. High levels of carbon dioxide i n the water reduce carbon
60 Chapter 2 Water Quality Water Sources 61
dioxide excretion at fish gills. This, in turn, causes the C02 concentration This composite carbonic acid concentration is in fact what is referred
in the fish blood to increase, lowering the blood plasma pH, which to as dissolved carbon dioxide. The acid--base equilibrium relationships
creates a condition called respiratory acidosis. When a fish is in this bet\veen pH and carbon dioxide in freshwater and seawater aquaculture
condition, the amount of oxygen that the blood hemoglobin can carry is systems have been extensively reviewed and a summary of the carbonate
reduced and respiration distress can occur, even with high concentrations acid-base system is presented in Table 2.7 (Grace & Piedrahita, 1994,
of dissolved oxygen in the water. This is referred to as the Bohr-Root Stumm and Morgan, 1981).
effect. An upper limit of 15-20 mg/L carbon dioxide is recommended as The carbonate system can be considered to be a volatile system or a
steady state maximum for finfish (see Table 2.2), although this non-volatile system depending on whether or not aqueous carbon dioxide
recommendation is poorly supported by research. Colt (2006) states that is allowed to exchange and equilibrate with atmospheric carbon dioxide,
water quality criteria for carbon dioxide cannot be made at this time, volatile being one that has equilibrated with the atmosphere. RAS's with
especially for warmwater species. As a management technique, higher medium or higher fish densities (> 40 kg fish biomass per m3) are
concentrations (60-80 mg!L) have a narcotic effect on aquatic animals considered non-volatile due to:
and are sometimes used on a temporary basis as an anesthetic to reduce • high production rate of C02
handling stress and during treatment procedures. There has also been • high solubility of C02
work to use high levels of carbon dioxide to force fish to swim through • relatively low degassing rate of C02 across the water surface in a
connecting pipes from one tank to another (The Freshwater Institute,
culture tank.
personal communication).
and water and the acid-base reactions determine the chemical form in g
which dissolved inorganic carbon is present in water. Dissolved carbon
dioxide concentration is therefore a function of pH and the total
dissolved inorganic carbon (CtC03) present in water, i.e., carbon dioxide
(C02), carbonic acid (H2C03), bicarbonate ions (HC03"), and carbonate
-
ions (CO/ ). It is more correct to write H2C03 for carbonic acid where
•
(2.5)
Water Sources 63
62 Chapter 2 Water Quality
-2
-2 I
I
I
-3
.) I
I
I
.. I
,' I
I
,' U -S
2 I
/
/ I
/ -6 � -
/ �---I-- 1-------+--�
//
I
/ I
/ -7
I
-/
/ I
-1
/
I I
-& +-------�--�--��--
8 10 ll ll
-8�1--- -�----�'��--+-�---'---�--� 10 11 12
pH
8
pH
Figure 2.3 Non-volatile (closed) log C-pH diagram for freshwater at 20 oc Figure 2.4 Volatile (open) Log C-pH Diagram for freshwater at 20 ° C and
(from Bisogni and Timmons, 1994). for an atmospheric C02 conecnttation of315 ppm (concentration of
J.s
1 o· atm) (from Bisogni and Tirrunons, 1994)
[H2C03 ·], can be calculated from the total carbonate carbon, [CtC03], as mg CaC03 per litcr.
and pH, since pH defines [I-t]: Applying the equilibrium constants given in Table 2.7 for C02 and
assuming a gas space concentration of C02 around the stripping device of
(2.6)
5,000 ppm (OSHA 8-hr limit, see Table A-15), we can calculate the
concentration of C02 in the water as follows:
- 11
_
L
·
(2.7 ) Table 2.7 Carbonate System Acid-Base Equilibrium Reactions and Equilibrium
Constants in Freshwater (Stumm and Morgan, 1 9 8 1 ) (square brackets
signify molar concentrations (moles/L); the units of the partial pressure of
carbon dioxide (Pco2) are atmospheres (atm) (from Surnmerfelt et al. 2000;
refer to Piedrahita and Seland, 1995; for temperature dependence of the
equilibrium constants.)
64 Chapter 2 Water Quality Water Sources 65
Equtlibrium • strong bases which do not contain any carbon, e.g., sodium
T e
Equilibrium Relationships Equilibrium Constants @ 25°C
hydroxide, and
eo, (g)+-+COz (aq) K" = Pco /Xco
2 2
Gas-liquid 6 . l l x l 0.. atm·•
•
�
bases that contain carbon, e.g., sodium bicarbonate.
hydration/
dehydration
COz (nq) + Hz0-H1CO, Ko � [H1COl]/[C01] = 1.58xi0·1
.
acid-base H1COJ+-+HCO.J 'H
.
K,- [H ][HCO;]/(H>COJ] - 2.83x I 0.. moVL In either case, the addition of bases causes an increase in the
acid a -b se
IIC0·3-CO 1+H
+
K2 •[COl.)[ll )I[HCOl.]
•
• 4.68xlo·" moVL
alkalinity of the culture water. In the case of the carbon-containing bases,
the increase in alkalinity is accompanied by an increase in total carbonate
acid-base H10+-+0H.+H• Kw =[OH-][H•] = I .OOxl(y•• moi1/L2
d is;olution/
caco)-co")+ea
++
K.,=[COl J[Ca l
++
= 4.57xl0" moi2/L2
9
carbon. The pH increase resulting from chemical base addition is
determined by the initial characteristics of the water (pH, alkalinity, and
precipitation
total carbonate carbon) and by the type and amount of base added.
Equations derived from the carbonate chemistry system, Table 2. 7, can
These equations illustrate that the dissolved carbon dioxide be used to target a design carbon dioxide concentration and the
concentration can be effected by changes in the total amount of corresponding alkalinity and carbonate carbon. The target of levels of
carbonate carbon in solution, the alkalinity, or the pH of the water. Note alkalinity and carbonate carbon can then be used to estimate the amount
that the hydration/dehydration reactions are semi-instantaneous while of base needed for maintaining the design carbon dioxide level.
the acid-base reactions are much slower (seconds). Chan es � in
temp�ralure and salinity can also have minor effects, since they affect the SALINITY
.
eqUlhbnum constant values (Piedrahita and Seland, 1995). In addition to
Water is commonly described as fresh, brackish, or saltwater. Each
these equations, an approximation within 5-10% can be used to calculate
of these terms refers to the salinity of the water, and there arc no clearly
the dissolved carbon dioxide concenu·ation given the alkalinity and pH
identified crossover points between these characterizations. Salinity is
(restricted to a pii range from 6.5-9.5; Summerfelt, 1996):
defined as the total concentration of dissolved ions in water, and is
usually reported as parts per thousand (ppt) or grams of salt per kilogram
of water. The major contributors of dissolved ions are calcium sodium
(2.8) potassium, bicarbonate, chloride, and sulfate. The salinity ;f natura i
waters tends to reflect the climate, geography, and hydrological
where: conditions of the immediate surroundings. Each aquatic species has an
optimum range of salinily fo.r rep.r.oduction and growth, although the
Cco, Dissolved carbon dioxide concentration (mg/L)
salinity tolerance of most aquaculture species is rather broad. For
ALK Alkalinity (as CaC03 mg/L)
example, rainbow trout fingerlings are produced in freshwater,
acclimated to saltwater and then can be grown out to marketable size in
Metho?s of C02 degass�g are presented and discussed in Chapter 8.
. sea cages at salinities as high as 20 ppt. Most freshwater fish of
The add1t10n of bases to tncrease the pH and shift the carbonate
commercial importance reproduce and grow well at salinities up to at
chemistry equilibrium will control carbon dioxide in aquaculture systems
least 4-5 ppt.
(Grace and Piedrahita, 1994; Summerfelt, 1996; Loyless and Malone,
Fish maintain the concentration of dissolved salts in their body fluids
1997). Typically adding bases to the culture water does not result in the
by regulating the uptake of ions from the environment and through the
removal of dissolved inorganic carbon from solution, but merely causes a
restriction of ion loss. This process is called "osmoregulation".
decrease in the carbon dioxide concentration by shifting the carbonate
Freshwater fish, for example, tend to accumulate water because they
carbon balance to bicarbonate and carbonate ions as the pH is increased.
have body fluids more concentrated in ions than the surrounding water.
Two general classes of chemicals are used in aquaculture to control
When exposed to salinity values outside of their optimum range, aquatic
pH and decrease carbon dioxide concentrations:
species must spend considerable energy for osmoregulation at the
expense of other functions, such as growth. If salinity deviates too far
from optimum, the animal cannot maintain homeostasis and dies. The
66 Chapter 2 Water Quality Water Sources 67
blood o f freshwater fishes has an osmotic pressure approximately equal DISSOLVED OXYGEN
to the osmotic pressure of a
7 ppt sodium chloride solution. Freshwater
Although dissolved oxygen (DO) cnn
aquaculture systems are generally maintained at 2-3 ppt salinity to
be measured analytically by using the
reduce stress levels and the amount of energy required for
Winkler Method and a simple titration,
osmoregulation, thereby increasing growth rates.
the dissolved oxygen meters available
today allow for rapid and accurate
SOLIDS - SETTLEABLE, SUSPENDED, DISSOLVED
analysis over a range from zero to
Waste solids accumulating in an aquaculture system come from supersaturation. Two types of electrodes
uneaten feed, feed fines, fish fecal matter, algae, and biofilm cell mass are commonly used: polarographic and
sloughed from biological filters. Studies indicate that fish produce galvanic. In simple terms, both of these
between 0.3 to 0.4 kg total suspended solids (TSS) for every 1 kg of feed meters consists of an electrode, which
fed. Waste solids influence the efficiency of all other unit processes in a produces a signal proportional to the
rccirculaling system. They are a major source of carbonaceous oxygen concentration o f the oxygen in the water, and instrumentation to convert
demand and nutrient input into the water, and can directly affect fish tbc signal reading to a visual display or recording device. A typical
health within rccirculating systems by damaging fish gills and harboring polarographic DO electrode or probe consists of a gold electrode and a
pathogens. The tentative upper limit for freshwater fish is 25 mg TSS/L, silver-silver oxide reference electrode. The electrodes are bathed in 4 M
with 1 0 mg TSS/L usually recommended for normal operation; tilapia KCl and separated from the sample by a membrane, usually made of
can perfom1 well with TSS levels of 80 mg/L if all other water quality Teflon, polyethylene, or fluoroc�rbon. The membrane is permeable to
parameters are at a preferred level. Therefore, solids removal is one of gases and the rate at which oxygen crosses the membrane is directly
the most important processes in aquaculture systems. Optimally, solids proportional to the dissolved oxygen concentration in the sample. When
need to be removed from the fish culture tank as soon as possible, while an electrical voltage is applied to the probe, molecular oxygen diffusing
creating as little turbulence and mechanical shearing as possible. across the membrane reacts with the cathode (gold ring) and a small
Solids are generally classified into three categories: settleable, current flow to the anode electrode (silver). In a galvanic system, the
suspended, and fine or dissolved solids. The difference between electrode generates a small voltage (mV range) proportional to the
settleable and suspended solids is simply the time it takes for them to dissolved oxygen concentration. Both systems require temperah1re,
settle to the bottom of an Imhoff cone. Settleable solids seule out in less atmospheri c pressure, and salinity compensation, usually accomplished
than an hour. Suspended solids do not; and therefore require a treatment by a combination of calibration and instrumentation hardware and
process other than conventional gravity settling basins. Fine and software. Currently there are numerous DO meters available, over a wide
dissolved solids are by their very nature difficult to remove. range of price scales. As usual, you usually will "get what you pay for",
so invest in a good oxygen meter (- $500 minimum).
The newest technology for measuring dissolved oxygen is based
2.6 MEASUREMENTS upon dynamic fluorescence quenching of a luminescent dye
(Luminescent Dissolved Oxygen, LDO). The sensor in the cap is coated
METERS & INSTRUMENTS with a luminescent material. Blue light from an LED illuminates the
The three water quality parameters described below are the three luminescent chemical on the surface of the sensor cap. The luminescent
most critical to successful aquaculture, in that they can change chemical instantly becomes excited and then as the excited chemical
dramatically in a relatively short time (DO can drop to lethal levels in relaxes, it releases red light. The red light is detected by a photodiode
minutes at high loading densities!). As a result, they should be monitored and the Lime it takes for the chemical to return to a relaxed state is
continuously, with backup systems and alarms to indicate out of measured. The higher the oxygen concentration, the less red light is
tolerance conditions. given off to the sensor and the shorter time it Lakes for the luminescent
material to return to a relaxed state. The oxygen concentration is
inversely proportional to the time it takes for the luminescent material to
68 Chapter 2 Water Quality Water Sources 69
retum to a relaxed state (www.Hach.com). A simulated in-house EPA less susceptible to clogging, needs no refilling with electrolytes, and
Tier 3 Validation Study (Jackson and Fair, 2004) results indicate the requires little or no maintenance..
LDO sensor procedure is superior in performance to EPA Winkler The following parameters are usually slower to change than the
reference method (EPA Method 360.2) and its allemative EPA approved parameters addressed above, and therefore can be monitored on a
membrane electrode method (EPA Method 360.1). periodic (usually daily or weekly) basis. Of course, monitoring frequency
Unlike electrochemical dissolved oxygen sensor technologies, the can be increased if necessary due to a significant operational problem.
LDO sensor does not consume oxygen. It does not require frequent
recalibration or frequent cleaning (except when associated with ORP (OXYGEN REDUCTION POTENTIAL)
consumptive slimes), resulting in longer sensor life and more stable and
Oxidation Reduction Potential (ORP or Redox Potential) measures
accurate readings. The system is also flow-independent so measurements
an aqueous system's capacity to either release or accept electrons from
can be made in applications with low or no flow.
chemical reactions (Walker, 2009). ORP is used just like p H to
characterize a systems water quality, but usually employed in
TEMPERATURE
aquaculture to control dosing of ozone. The ORP sensor works similarly
Traditionally, temperature was measured with a simple mercury to a pH probe using a two-electrode system that makes a potentiometric
thermometer. Recently, these are becoming harder and harder to obtain, measurement expressed as either a positive or negative millivolts (mV).
due to the significant environmental harm (and potential economic A solution with a positive ORP measurement will gain electrons (i.e. be
hardship) it will do if broken and mercury is released into the reduced by oxidation) and a solution with a negative ORP will lose
environment (or in some cases, the production tank!). Thankfully, there electrons (i.e. be oxidized by reducing the new species). Although
arc a host of alternative measurement devices, and most of them are measurement of ORP is relatively' straightforward, differences between
more convenient and flexible in their use. To start with, most DO meters laboratory and in-plant sampling can vaty significantly due to the effects
and pH meters have some form of built-in temperature measurement for of solution temperature and pH, the slow electrode kinetics, electrode
calibration and temperature compensation. Second, simple handheld poisoning, and the small exchange currents leading to drift and poor
temperature meters are relatively cheap, accurate, and easy to use. response. Still ORP measurements have proven useful as an analytical
Finally, these types of temperature measurements allow for easy data tool in monitoring changes in a system rather than determining their
logging and control. absolute value for example controlling the dosing of ozone.
PH CARBON DIXOIDE
Like the dissolved oxygen meters, easy to read pll meters are available Several types of dissolved carbon dioxide meters have recently become
over a wide range of specifications and price. In addition to pH, most pH available. These work by first measuring the pH of the solution, and then
n meters arc also capable of measuring calculating the C02 concentration based on the alkalinity (which must be
other ion specific electrodes, which known) and the carbonate equilibrium relationships. If the alkalinity is
include such parameters as ammonia, relatively constant, then C02 levels can be easily monitored and
nitrate, Oxygen Reduction Potential, controlled by simply measuring the pH.
dissolved oxygen, conductivity, among Carbon dioxide is usually measured by titration of a water sample to
others. However, please keep in mind the phenolphthalene endpoint (pH 8.3) with a standard base.
that most of these ion specific electrodes Approximate C02 concentrations can be determined from known values
were designed to be used under of pH, tcmpernture, arrcf afkaTinity using either a formula or table values
laboratory conditions and require some (see Fig. 2.2).
sample pretreatment, and they are limited
to specific ranges of concentration. It is recommended that a
combination, gel-filled pH probe be used. This instrument is inexpensive,
70 Chapter 2 Water Quality Water Sources 71
SALINITY requires very little expensive laboratory equipment, and does not
generate large quantities of hazardous wastes. Table 2.8 provides a
Salinity can be indirectly
summary of methods.
measured using the
measurement of a physical
DISSOLVED OXYGEN (DO)
property such as refractive
index, conductivity, or density. In the basic Winkler method, a sample of water is treated with
Of these, the two most manganous sulfate, potassium iodide, and sodium hydroxide. Under
commonly used in aquaculture are the refractive index and conductivity these highly alkaline conditions, the manganous ion is oxidized by the
measurements. A refractometer utilizes a change in the refractive index dissolved oxygen to manganous dioxide. Sulfuric acid is then added to
as function of the salt concentration to directly dissolve the precipitate and produce acid conditions for the oxidation of
display the salinity level. It is very simple to use. iodide to iodine by manganous dioxide. The quantity of iodine released is
Simply place a drop of water on the window and proportional to the amount of dissolved oxygen (DO), and is estimated
look through the eyepiece to directly read the by titration with standard sodium thiosulfate with a starch indicator as
salinity in parts per thousand. Refractometers the endpoint. This sounds difficult, but in practice, all of the reagents are
provide fast, accurate salinity measurements, but available in a premixed form in many commercially available test kits
some form of temperature-compensation is and thus DO measurement is a routine activity. With the availability of
recommended when used outside their normal relatively low cost dissolved oxygen meters, this method is usually used
operating range of 20°C. One problem they do only for cross checking and calibrat_ion purposes.
have is that most commercially available models
have a wide salinity range of 0-100 ppt, making accurate measurements Testing Procedures for DO Transfer. Standard tests for aerators are
at low salinities difficult. conducted using clean tap water at standard temperature and pressure
Electrical conductivity measurements can also provide a simple and (20°C and 760 mm Hg). Tests are based upon using deoxygenated water
quick measurement of salinity. Conductivity meters measure the flow of that has had the DO removed using a sodium sulfite (Na2S03) solution
electrical current between two electrodes submersed in water, which is using cobalt chloride (CoC12·6H20) as a catalyst. The theoretical
directly proportional to the concentration of ions, i.e., salts, in the water. requirement for deoxygenation is 7.88 mg/L of sulfite (as Na2S03) per
They can be very accurate over a wide range of concentrations; these 1 . 0 mg/L of 02 removed. The cobalt chloride should be used at a
meters are direct reading and very portable. concentration of 0 . 1 0-0.50 mg/L (as Co). A slightly higher concentration
Hydrometers measure salinity based on changes in water density may be required if the water temperature is below 1 ooc. For more
(specific gravity) as a function of salinity. However, accurate and reliable details, see APHA (1995).
hydrometers are more expensive
than refractometers or electrical
conductivity meters that provide the same degree of accuracy and ease of
C02
use, so they are typically not used. Inexpensive hydrometers are not
recommended at all except for very gross estimates. The simplest method of determining carbon
dioxide concentration in the water column is to
specified volume of sample water (normally, 250 mL). Since water at a Table 2.8 WaterQualityParameters: Standard Methods
pH over 8.34 does not contain appreciable amounts of carbon dioxide, Water Quahty Standard Methods
Parameter Monitoringmethod
the amount of a base (normally, sodium hydroxide) needed to raise the Temperature 2550 Temperature
sample's pH to the 8.34 pH endpoint is approximately equivalent to the Temperatures are traditional made with mercury-filled thermometers, but
carbon dioxide content of the sample. Free carbon dioxide reacts with non-mercury or electronic temperature meters are preferred due to the
toxicity of mercury in the environment.
sodium to form sodium bicarbonate, which raises the sample's pH. Thus, pH pH Meters
sufficient amounts of the titrating solution of sodium hydroxide are Follow manufacturer's instructions for calibration using kno\\n standards
added to raise the sample's pH to 8.34. The quantity of sodium hydroxide 4.0, 7.02 and I 0.
that was required to reach this endpoint is equal to the amount of C02 in
Total Suspended 2540 Solids
Solids A well-mixed sample is filtered through a weighed standard glass-fiber
the sample, because l mL of sodium hydroxide (0.0227 N strength filter and the rc:.icl. ue retained on the filter is dried to a constant weight a t
titrating solution)) equals 1 mg!L C02 concentration in the sample. I 0 3 to I 05 •c. The increase in the weight of the filter represents t h e total
suspended solids.
4500- NHJNitrogen (Ammonia)
ALKALINITY
Ammonia
Colorimetrie Ne:.slerization Method: nessler-ammonia reaction produces a
yellow to brown color, measured with spectrophotometer at 425 nm.
Alkalinity is a measure of the acid neutralizing capacity of the water. Nitrite 4500-N02•Nitrogen (Nitrite)
Alkalinity can be measured by titration with 0.02 N sulfuric acid and Colorimetric method with diazotized sulfanilamidc with NED
titrating to a pH end-point or using a phenophalein indicator to show the dihydrocbloridc creating a reddish purple azo dye measure with a
>pcctrophotometer at 543 nm.
calor change as the indicator to stop adding titrant. With a 0.02 N
Nitrate 4500-NoJ· Nitrogen (Nitrate)
sulfuric acid, one mL of titrant equals 1 0 mg/L of alkalinity (defined as
calcium carbonate, CaC03). Only a few items are required to perform
Cadmium reduction to nitrite and measurement ofN�·.
acid (available premixcd), methyl orange indicator, and a dropper. heteropoly acid. which is reduced to an intensely colored molybdenum
blue by ascorbic acid.
Alkalinity 2320-Titration Method
Titration with 0.02 N Sulfuric Acid with methyl orange indicator end
point (4.5 pi 1), I mL titrant equals I 0 mg!L CaCOJ.
Hardness 2340 Hardness
EDTA titri mctric method using EDTA and ethylenediaminetetraacetic
acid and Calmagite. Titrated with EDTA from a red to a blue color.
weight by the volume of sample. The result is the total suspended solids Grace, G.R., Piedrahita, R.H., 1994. Carbon dioxide control. In: M.B.
concentration (mg/L). Timmons and T.S. Losordo (Eds.), Aquaculture Water Reuse
Settleable solids are measured with an lmhoff cone, which is a cone Systems: Engineering Design and Management, Elsevier Science,
shaped container with volume gradations at its base. A sample of 1 L is Amsterdam, NY, pp. 209-234.
poured into the Imhoff cone and allowed to settle for one hour, after Jackson, C.B., Craig, E., Fair, C., 2004. Contrasting Methods for the
which the volume of settleable solids in the base of the cone are read in Measurement of Dissolved Oxygen: a Case for Luminescent
mLIL. Dissolved Oxygen Sensors. Water Environment Federation.