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CHEMICAL PARAMETERS

pH

Background/Rationale: The alkalinity of a water is a measure of its capacity to accept protons


or to neutralize an acid. It is caused mostly by presence of bicarbonates, carbonates, and
hydroxides and to some extent by borate, silicate, and phosphate. Highly alkaline waters are
usually unpalatable and not used for domestic water supply. Organisms only have certain limits
of tolerance to excess base and since it affects water pH, the various parameters and treatment
processes like chemical coagulation, water softening, and corrosion control may also be affected
by pH and hence also by excessive amounts of alkaline materials.

The acidity of a water is the capacity of that water to donate protons or to react with a base. This
ability may be due to carbon dioxide dissolved as carbonic acid to unionized portions of weakly
ionizing acids such as acetic acid, humic acid, and tannic acid produced from decomposition of
organic matter and to mineral acidity from hydrolyzed salts of ferrous or aluminum sulfate. As
water precipitates in the form of rain, it dissolves with it impurities and atmospheric gases
including carbon dioxide. More carbon dioxide dissolves in the water as it percolates to the soil
or as it flows as surface runoff. Carbon dioxide may also be produced in the water from
biological oxidation of organic matter and from respiration by aquatic organisms.

The bottom layer (hypolimnion) of most lakes are rich in carbon dioxide due to both aerobic and
anaerobic decomposition of organic matter by aquatic microorganisms. Ground water coming
from water that has percolated through soils that do not contain enough calcium or magnesium
carbonate to neutralize the carbon dioxide through formation of bicarbonates may add to
carbon dioxide concentration of ground water mixing with lakes or river waters.

Mineral acidity is usually contributed by industrial wastes especially those related to


metallurgical and mining industries (e.g., sulfuric acid or salts of sulfuric acid if sulfur, sulfides, or
iron pyrites are present). Salts of heavy metals especially those of Fe+3 and Al+3 hydrolyze in
water to release mineral acidity. Organic acids may also come from industries or from
decomposition of organic matter by microorganisms.

For aquatic organisms, certain high acidity may cause irritations, especially of the eyes and
mucous membranes.

pH measurement in limnology is usually done either colorimetrically or electrometrically. The


colorimetric method is based on the fact that certain organic compounds change color as pH of
the surrounding medium changes. The colorimetric method requires less expensive equipment
and can be easily used in the field but it suffers from severe interference contributed by color,
turbidity, high saline content, colloidal matter, free chlorine, and other oxidants and reductants
which would affect the color of the dye. The indicators are subject to deterioration, as are the
color of the standards with which they are compared.

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


The pH of a solution can be measured electrometrically by means of an electrometer (pH meter)
connected to two electrodes (or one electrode in which both are combined) that are immersed
in the solution. The glass electrode system is based on the fact that a change of 1 pH unit
produces an electrical change of 59.1 mV at 25 °C (i.e., the electrical potential developed at the
electrode depends upon [H+] concentration). The interferences mentioned in the colorimetric
method are not experienced with the electrometric method.

Technique: Electrometric measurement

Protocol:

Materials: meter sticks, tape measures or transect, pH meter, sampling bottles

Procedure:
 Identify the water depths and representative points in your station wherein pH readings
would be collected. Assign 3 points along the water column (i.e., various depths) and 3
representative points in your station. Note the depths wherein you collected pH
readings, as well as the representative points (mark these points in your morphometry
diagram). Do not immerse the pH meter in the water. Use sampling bottles to collect
the water at various depths, then measure the pH readings from these samples.
 Report mean pH readings (from 3 trials per sampling point) per hour.

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


DISSOLVED OXYGEN

Background/Technique: Dissolved oxygen (DO) analysis of surface waters and waste waters
provides important information on the biological and biochemical reactions going on in these
waters. The amount of dissolved oxygen directly affects the aquatic life, especially those
dependent on aerobic respiratory reactions for energy production needed for different synthetic
activities, growth, and reproduction. The amount of dissolved oxygen in natural waters also
determine the capacity of water to receive organic wastes without causing nuisance or killing
aquatic life.

The atmosphere consists of about 21% oxygen and it can dissolve freely in fresh waters. The
amount of oxygen that can dissolve in water is however limited because it does not react with
water chemically and hence does not exist in half bound or bound forms similar to carbon
dioxide. Since it is a poorly soluble gas, its solubility varies directly with the atmospheric
pressure at any given temperature. This may be of consideration for rivers and lakes in high
altitude. Oxygen solubility is also dependent on temperature, and since biological oxidation rate
increases with temperature, DO concentrations may become critical under such conditions. Thus,
during summer months, decrease in DO concentrations may be responsible for fish deaths in
lakes. Low oxygen solubility in natural waters also limits the self-purification capacity of surface
waters and therefore limits the amount of decomposable wastes that can be discharged into
them.

Aside from atmospheric source, DO is mostly contributed by aquatic plants, especially algae,
during photosynthesis (from the hydrolysis of water during the light reaction). However, the
same plants will also utilize the oxygen present for their respiratory needs. Algal bloom may
cause supersaturation of DO during the day, but their respiratory requirements in the evening
may not be supplied by the reserved DO and hence may again cause fish kills. Also, when the
algae in algal blooms start to die and decompose, great amount of oxygen may be needed for
their stabilization and lead to reduced DO concentrations of rivers and lakes. Presence of
thermal pollution will also reduce water DO. High concentrations of ions (salts) in the water also
tend to diminish the amount of DO.

Determination of DO serves as the bases of the Biological Oxygen Demand (BOD) test, which is
a measure of the polluting capacity of wastes. It determines the amount of oxygen required for
aerobic decomposition of a given waste by microorganisms. The rate of biochemical oxidation
can be evaluated by determining residual DO in a sample or system at various time interval of
incubations.

Care must be exercised in the collection of sample to be analyzed for DO. In most cases, the DO
present in natural surface waters will be below saturation level and so their exposure to the air
during sampling would lead to erroneous higher DO values. If space is available so that the
bottles are allowed to overflow, a sample of water that is representative of the mixture being
sampled can be obtained. Most of the samples for DO test may be collected in the field.
Nevertheless, since DO values may change due to biological activity in the sample or due to

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


temperature change, it is advisable to “fix” the samples immediately after collection. As
additional precautionary step, samples may be stored in the dark on ice until analysis can be
done.

Technique: Electrometric method

Materials: meter sticks, tape measures or transect, DO meter, sampling bottles

Procedure:
 Identify the water depths and representative points in your station wherein DO readings
would be collected. Assign 3 points along the water column (i.e., various depths) and 3
representative points in your station. Note the depths wherein you collected DO
readings, as well as the representative points (mark these points in your morphometry
diagram). Do not immerse the DO meter in the water. Use sampling bottles to collect
the water at various depths, then measure the DO readings from these samples.
 Report mean DO readings (from 3 trials per sampling point) per hour.

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


BIOCHEMICAL OXYGEN DEMAND (Optional: requires 5-day incubation period)

Background/Rationale: Biochemical oxygen demand (BOD) is the amount of oxygen required


by microorganisms (usually, bacteria) for the degradation or decomposition of organic matter
under aerobic conditions. The BOD test is widely used to determine the pollutional strength of
domestic and industrial wastes in terms of the oxygen they would require if discharged into
natural water courses where aerobic conditions exist. It is useful in determining the degree of
pollution of streams and lakes at any time and hence can be used in evaluating the purification
capacities of bodies of water receiving organic wastes.

The BOD test is a form of bioassay performed under standardized laboratory conditions; hence,
it is of limited value in measuring actual oxygen demand of surface waters. Moreover, the
extrapolation of test results to actual stream oxygen demand must be done with caution. The
laboratory conditions under which the test is performed do not approximate the stream
conditions specially with regards to temperature, sunlight, organisms present, water movement,
and degree of oxygen saturation.

The incubation period of the test was standardized to 5 days and results are expressed in terms
of 5-day BOD. Complete stabilization of a given waste may however require a longer period of
incubation (20 days to 1 month) which is impractical for analytical purposes.

The BOD reaction is closely related to a first-order type of reaction for the amount of organic
matter oxidized after a time t, (At) is equal to: At = Ao e–kt, where Ao is the original amount, e is
the base of the natural logarithm and k is a decay constant. A plot of the amount of organic
matter remaining vs time yields a parabolic curve. A reciprocal parabolic curve is obtained when
the amount of organic matter oxidized is plotted against time.

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


Figure 1. Changes in organic matter during biological oxidation of polluted waters under aerobic
conditions (figure adapted from Umaly and Cuvin, 1988).

Since the oxygen used is directly proportional to the amount of organic matter oxidized
biochemically, a plot of oxygen used versus time should also produce a parabolic curve similar
to the amount of organic matter oxidized versus time.

Figure 2. The BOD curve. (a) Normal curve for oxidation of organic matter. (b) The influence of
nitrification.

Technique: Dilution method

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


CHEMICAL OXYGEN DEMAND (Optional)

Background/Rationale: The chemical oxygen demand (COD) test provides a measure of the
oxygen equivalent required to degrade organic matter to carbon dioxide and water by a strong
chemical oxidant. It is based on the fact that all organic compounds, with few exceptions, can be
oxidized by the action of strong oxidizing agents under acidic conditions. Hence, similar to BOD,
it can also be used in determining the pollutional strength of domestic and industrial wastes.
The method is quicker (about 3 h) compared to the 5-day incubation period required in
determining BOD. Unlike BOD, it can be done even in the presence of toxic materials in the
sample. However, the test does not differentiate between organic material that is actively
biodegradable and not. In the absence of a catalyst, however, the method fails to include some
organic compounds that are biologically available to stream organisms, while including some
biological compounds (e.g., cellulose) that are usually not immediately available to
microorganisms and thus do not form part of the immediate biochemical load on the oxygen
supply of the receiving water. It also does not give an idea of the rate of biochemical
degradation of the wastes in nature.

Technique: COD Determination through redox reactions

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


NITROGEN (Optional: samples must be processed within 24 hours, or must be frozen in
the dark until processing)

Background/Rationale: Nitrogen exists in surface waters in various forms (e.g., organic or


inorganic; dissolved, colloidal, or particulate) and in different valence states. The change in state
and valence is usually brought about by living organisms, especially some groups of
microorganisms under aerobic or anaerobic conditions. The atmosphere is the major reservoir of
nitrogen (78% N2). However, even if its partial pressure is much greater than that of O2 and CO2,
its solubility in water is much less.

Analysis of nitrogen in various forms may serve as a basis of judging the sanitary quality of
water. Presence of high organic nitrogen is correlated with the presence of organic material that
could exert oxygen demand. High concentrations of ammonia and nitrite means that anaerobic
or reducing condition predominates in the water. A large quantity of nitrates means that organic
matter has already been established into a form that can easily be assimilated by algae and
aquatic plants. This may lead to heavy algal growth and hence to eutrophication of lakes.

The process of self-purification of streams and lakes can also be monitored using the tests for
various forms of nitrogen.

Technique: Titration

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


PHOSPHATE (Optional: samples must be processed within 24 hours, or must be frozen in
the dark until processing)

Background/Rationale: Phosphate and nitrate concentrations in lakes are the most important
chemical parameters that influence the rate of lake eutrophication. Phosphates play an
important role in biological metabolisms. The amount of phosphate in natural waters is usually
limited, although domestic sewage and waste containing detergents may increase phosphate
concentration in rivers and lakes. There is a complex rapid cycling of phosphorus, most of which
is within living organisms, primarily algae.

Technique: Titration

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


IRON (Optional: samples must be processed within 24 hours, or must be frozen in the dark
until processing)

Background/Rationale: Iron is the most abundant metal present in soils but in spite of its wide
distribution, surface waters normally have only minimal amounts in solution. Acid waters tend to
have higher quantities of iron compared to alkaline ones.

Technique: Gravimetric (precipitation) methods (for higher concentrations), colorimetric


methods (for lower concentrations)

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


MANGANESE (Optional: samples must be processed within 24 hours, or must be frozen in
the dark until processing)

Background/Rationale: The behavior of manganese in surface waters is very similar to that of


iron. In the hypolimnion, where bacterial decomposition is extensive so that carbon dioxide
concentration is high, the manganese concentration in solution may be high. However, as it
diffuses in the meta- and into the epilimnion, different stages of oxidation may be found and
resedimentation into the hypolimnion may occur.

Technique: Gravimetric methods

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


SULFATE (Optional: samples must be processed within 24 hours, or must be frozen in the
dark until processing)

Background/Rationale: The sulfate ion is one of the major anions in natural waters. It may
come from the soil as part of the sulfur biogeochemical cycle. Rivers and lakes may receive mine
drainage wastes containing sulfates from pyrite oxidation. Surface waters high in calcium or
magnesium sulfate may have cathartic property when used as source of domestic water supply.
They may also form scales in boilers and heat exchangers together with the carbonates. Sulfates
can serve as source of oxygen (i.e., as an electron acceptor) for biochemical reactions mediated
by anaerobic bacteria in which the sulfate is reduced to sulfide and an equilibrium may be
established with hydrogen to form hydrogen sulfide.

The hydrogen sulfide produced is responsible for the bad odor that may emanate from the
hypolimnion or in sewage treatment plant.

Technique: Gravimetric method, turbidimetric method

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


CHLORIDE (Optional: samples must be processed within 24 hours, or must be frozen in the
dark until processing)

Background/Rationale: Chloride is one of the major anions of lake and river waters especially
where there is considerable intrusion of sea water or where great amount of domestic and
abattoir wastes are discharged.

The amount of chlorides present in inland waters would also vary with the amount of mineral
content dissolved from topsoil and other land formations. Spray from the ocean may be carried
inland and contribute to chloride content of inland waters. The salty taste produced by chloride
concentration is variable and it depends upon the chemical composition of the water.

The amount of chlorides is sometimes mistakenly equated salinity. The salinity of inland waters
is contributed not only by chlorides but also by four other major cations (Ca++, Mg++, Na+, K+)
and major anions (CO3-2, HCO3-, SO4-2) the concentration of these ions together with chloride
constitute over 99% of the total salinity. Freshwater organisms differ in their tolerance for salt
concentration depending upon the efficiency of their osmotic pressure regulating mechanism.
Stenohaline organisms are those with narrow range of salinity tolerance.

Technique: Gravimetric methods

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


SILICA (Optional: samples must be processed within 24 hours, or must be frozen in the
dark until processing)

Background/Rationale: Silica ranks next to oxygen in abundance in the lithosphere and form a
common constituent of igneous rocks, quarts, and sand. It is required in the formation of
frustules of diatoms and the formation of spicules by freshwater sponges. Thus the amount of
free silica in water is usually only small to moderate as most of it are in rocks or in diatoms and
sponges. Silica occurs in dissolved form as silicic acid. Particulate silica are found in the
previously mentioned living organisms or absorbed to inorganic particles or complexed
organically. Complexes of silica with iron and aluminum decreases the concentration of soluble
silicates in the sediments. Water in contact with volcanic rocks tend to have high silica contents.

Silica contents of rivers tend to be uniform but those of lakes frequently exhibit marked
variation with season and in spatial distribution. This may be greatly dependent on degree of
diatom growth. A large diatom population in the epilimnion would reduce silica content of the
water and increase concentration in the sediments of the hypolimnion with sinking or death of
diatoms.

The rate of release from the sediment is dependent upon temperature and the difference in
silica concentrations between the sediment and the overlying water. Some of the sedimented
diatom frustules are lost permanently from the system and gets deposited as part of
diatomaceous earth. This is specially true in deep hypolimnion with quiescent waters.

Technique: Gravimetric method or colorimetric method

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


HARDNESS (Optional)

Background/Rationale: The term “hardness” originally refers to the capacity of water to


precipitate soap. Dissolved ions principally calcium and magnesium combine with soap to form
insoluble precipitates and thus delay the formation of suds until such combination is complete.
Precipitated materials (scales or incrustations) are also formed in vessels or tubes when water is
heated. For limnologists knowledge of the hardness in water provides information as to the
quantity of carbonates that could be used as reserved source of carbon dioxide for
photosynthesis. Hardness is also intimately associated with alkalinity. Aside from calcium and
magnesium other polyvalent metals like aluminum, iron, and strontium, manganese, and zinc
also contribute to hardness but since their natural concentrations in inland waters are low, their
contributions are generally considered insignificant compared with calcium and magnesium.
These cations are usually combined with bicarbonates and carbonates and can be precipitated
by boiling and are therefore considered as temporary hardness.

Technique: Titrations

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016


GREASE (Optional)

Background/Rationale: Grease has been singled out among the pollutants because of its poor
solubility in water and its tendency to separate from aqueous phase and thus float on the water
surface. Greases and oils are particularly resistant to anaerobic digestion and thus cause scum
formation on shoreline deposits. This reduces the amount of light that can penetrate the water
and lessens solution of needed gases. Wastes from meat packing industries, from
slaughterhouses, and leakage from boats are among the common sources of grease in lakes and
rivers. Removal of grease is also a problem in sewage treatment plants.

The term “grease” applies to a wide variety of organic substances that are extracted from
aqueous solution or suspension by hexane. Hydrocarbons, esters, oils, fats, waxes, and high
molecular weight fatty acids are the major materials dissolved by hexane.

The method of grease determination by hexane extraction does not include low-molecular
weight hydrocarbons such as gasoline. Prior to extractions, the sample is dried to 103 °C and
thus materials whose boiling points are below this temperature are lost. Also, materials that
have appreciable vapor pressures at 103 °C would also be lost. However, most of the “grease” in
natural waters and domestic wastes have low vapor pressure at 103 °C and are therefore almost
completely recovered. Exception is if petroleum industry wastes are present.

The method suggested is suitable for biological lipids and long-chain mineral hydrocarbons.

Technique: Hexane extraction

Prepared by P San Jose | Bio 164 1st Sem AY 2015–2016