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Related FAQs: pH,
Alkalinity, Marine Alkalinity,
Marine Alkalinity 2, Marine Alkalinity 3, Marine Alkalinity 4, Calcium and
Alkalinity, & FAQs on: The
Science of Alkalinity, Importance,
Measure, Sources, Use of
Additives/Buffers, Troubleshooting/Fixing, Products by Name: & FAQs on pH: Importance,
Science, pH
Measure/Test Gear, pH Controllers &
pH Buffers/Buffering, pH Anomalies
(Troubleshooting/Fixing), &
pH Products by Name, Manufacturer,
& FAQs on: The Science of Calcium
& Alkalinity, Importance,
Measure, Sources, Use of
Additives, Troubleshooting/Fixing, Products,
Related Articles: Marine Maintenance,
Water Quality, Understanding Calcium &
Alkalinity, Understanding Calcium
& Alkalinity, Biominerals, Using Kalkwasser, Calcium Reactors, Marine Maintenance,
Marine Water Quality,
Magnesium in Seawater, Strontium in Seawater,
* excerpted from the Book of Coral
Propagation, Volume 1 by Anthony Calfo Alkalinity: The
Buffering Ability of Seawater
Alkalinity
for Marine Systems
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by Anthony Calfo
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"Alkalinity and pH are distinctly different from each other,
although their definitions and functions can be easily confused. For
those of you as uninformed about water chemistry as I was when I first
began, alkalinity is essentially a measurement of water's ability
to neutralize acids. It is a measure of the buffering capacity of a
system while pH is basically the measurement of the concentration of
hydrogen ions in water, in terms of acidity or alkalinity. The
alkalinity of water regarding pH issues merely refers to the basic end
of a pH scale (alkaline) in contrast to the acidic end of the scale and
does not reflect the buffering capacity of a system. It is easy to
believe that water with alkaline pH is likely to be high in alkalinity
(buffering capacity). However, this is not necessarily true. Water with
a high pH, but a low alkalinity is regarded as unstable. Such water
will quickly decline in pH with the natural accumulation of organic
acids in aquarium systems. Regarding the care of reef invertebrates,
water that is low in alkalinity but high in pH is generally
undesirable. Unfortunately, it is not uncommon for aquarists to test
their systems and report such conditions. Alkalinity depletion is
caused sometimes by the misapplication of calcium supplements and/or a
lack of water changes. It occurs naturally, as stated, from the
neutralization of acids and removal of carbonates for calcification
primarily. Ironically, it is obvious to aquarists that corals need
calcium to grow, but carbonates are often ignored. Calcium supplements
are some of the first and only products that many aquarists use for
reef invertebrates culture. It is often forgotten, however, that coral
skeletons are comprised of calcium carbonate. Calcium additions without
balanced carbonate additions are about as useless as the keys to one
thousand cars in an empty parking lot. And so, misinformed aquarists
may continue to dose calcium without noticing any significant growth
among corals in the collection (and in observance of an alkalinity that
continues to fall). To some extent, an imbalance between free calcium
and carbonate levels is natural, although unfriendly at times to
successful reef aquariology. Grossly stated, high alkalinity and high
calcium levels are mutually exclusive. Simply stated, seawater can only
hold so many dissolved solids. As alkalinity increases (the levels of
carbonates and bicarbonates) there is less "room" for the
saturation of other dissolved elements such as calcium. Calcium and
alkalinity in practical applications exist in a tenuous Hi-Lo
relationship. Until recently, systems with high alkalinity and low
calcium were uncommon because of a poor understanding about alkalinity
and the popular application of calcium supplements. The advent and
success of calcium reactors has made some aquarists change their
thoughts on ways to maximize calcification. Aquarists are divided on
which Hi-Low methodology for maximum calcification works best. Some
aquarists dose kalkwasser aggressively to raise calcium levels and
accept the coincident drop depression of alkalinity. This technique has
grown many corals to impressive size with numerous other benefits from
the supplementation of calcium hydroxide. The intent of some aquarists
is to maintain calcium levels above 400 ppm. As such, calcium
hydroxide indirectly contributes to the alkalinity of a system by
neutralizing acids that would otherwise exhaust buffers from the
system. Hydroxide molecules are "spent" rather than carbonate
molecules. And so, high calcium and adequate alkalinity can be
maintained with the proper application of kalkwasser. While I am
inclined to favor this technique for simplicity and the small expense
incurred relative to reactor set-ups, it is admittedly difficult to
maintain and potentially dangerous when pushed to extreme. It is an
error to think that if the addition of x grams of calcium is a good,
then 2x grams are better. At calcium levels extending beyond
saturation, or during events when calcium is added quickly, it is
possible to disturb the balanced relationship between calcium and
alkalinity and cause a sudden precipitation of calcium carbonate,
commonly known as a "snowstorm", which can have tragic
ramifications. Spontaneous precipitation of calcium carbonate occurs
when pH levels rapidly climb beyond a certain threshold, which causes
crystalline carbonate "snow" to fall out of solution in
an essentially insoluble form. The tragedy of the event for a system
suffering from this condition is that the reaction must run its course
before corrective measures can be taken. The addition of buffers in an
attempt to counter the declining alkalinity serves only to feed the
precipitous reaction. An aquarist is resigned to watch the spawn of his
error to completion, which leaves the buffering capacity of the system
at a dangerously low level. The stress of the sudden change in
water quality can be significantly harmful to marine organisms as well.
Water changes and any methods of damage control that insure stability
in the environment will be necessary. Despite the inherent risks, I
strongly favor and recommend the use of properly dosed calcium
hydroxide in at least small quantities for most systems. One of
the very best ways to maintain alkalinity in reef invertebrates systems
is the employment of a calcium reactor. Calcium reactors are vessels
filled with calcium carbonate material that is slowly dissolved with a
supply of carbon dioxide. Lingering or accumulating carbon dioxide in
aquarium systems depletes alkalinity and lowers pH, as the presence of
carbon dioxide is neutralized by carbonate ions in seawater. It can
also contribute to undesirable growths of algae if neglected. Carbon
dioxide and carbonic acid in solution are easily driven off with
vigorous aeration. Properly operated, calcium reactors do maintain high
alkalinity and reasonably good calcium levels (although they are
significantly and proportionately lower). Although they are no less
dangerous to use than calcium hydroxide for supplying calcium and
alkalinity, calcium reactors are convenient and efficient devices. I
strongly recommend the use of calcium reactors for aquarists favoring
stony corals in display or culture, and for aquarists displeased with
the tedious application of calcium hydroxide. Calcium hydroxide,
however, does have additional benefits such as saponification
(improving protein skimmer performance) and phosphate precipitation.
Many European hobbyists rely on calcium reactors to maintain high
levels of alkalinity with supplementation from calcium hydroxide. This
has proven to be an excellent methodology for promoting the growth of
calcareous organisms. The oldest and most common method of increasing
the buffering capacity of salt water is the addition of sea buffer. Sea
buffer is basically (no pun intended) a powdered mix of bicarbonates,
carbonates, and borates. Such mixes are designed to increase the
alkalinity (buffering capacity) of seawater without raising the pH
beyond a set point. Some buffering products do raise the pH of seawater
and should only be used with caution. Baking soda, sodium bicarbonate,
is a significant portion of most dry mixes of sea buffer. I do not
recommend using sodium bicarbonate alone for most aquarists, especially
new and less experienced individuals, without the strong admonition
that it can raise pH quickly and dangerously without due caution.
Baking soda should only be used in small portions when water quality
can be tested frequently. Concentrated liquid buffer solutions are
becoming popular and seem to be most useful when dosed with
proportionate amounts of calcium supplementation in commercial two-part
mixes. It is recommended that alkalinity in captive systems be
maintained between 7-12 dKH. There are, in fact, several ways to test
for alkalinity in seawater. Some aquarists prefer to measure alkalinity
in milliequivalents per liter [meq/L] (the target is more than 3
meq/L). Buffering capacity is also described as carbonate hardness,
measured in ppm, but this is only a measure of carbonates and
bicarbonate components. Total alkalinity measures all buffers and
is higher than carbonate hardness. Commercial test kits for testing
alkalinity are sometimes difficult to read. Aquarists who have color
blindness, vision impairment or other difficulties in reading
colorimetric charts should consult distributors or fellow aquarists
(marine aquarium societies, Internet, etc.) on brands of test kits with
conspicuous color changes at the titration point. Lastly, there are
implications that difficulties maintaining calcium and alkalinity may
be linked to inappropriate magnesium levels. Magnesium should be
maintained at roughly three times the level of calcium. High magnesium
levels are encountered by inappropriate supplementation and can be
lethal to some reef invertebrates. Aquarists have most often reported
sensitivity in mollusks and starfish such as "turbo" snails
and brittle/serpent starfish. Low magnesium levels, as in economy brand
synthetic sea salts have likewise been implicated in difficulties
maintaining free calcium and alkalinity adequately. This is yet another
reason for maintaining proper water quality through water exchanges and
testing with supplementation."
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