CHEMISTRY
AND THE AQUARIUM by RANDY HOLMES-FARLEY, Ph.D.
Sponsored
in part by:
Strontium
and the Reef Aquarium
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Much has been
written about the need for strontium in reef aquaria. Some
authors have described it as an important additive,1
while others have described it simply as a poison.2,3
Why are there such divergent opinions on strontium? Partly
this is because there have been few, if any, scientific studies
of the effects of depleted strontium on organisms that most
reef aquarists maintain. Partly too it may be because many
aquarists confuse the idea that an organism “needs”
an ion in solution with the idea of “needing a supplement.”
Finally, I think many authors have, perhaps incorrectly, extrapolated
observations from one or more reef aquaria to others that
may have a totally different strontium balance.
This article on
strontium is the second of several that delve into a variety
of issues involving magnesium and strontium. Calcium, magnesium,
and strontium are very similar chemically. So similar, in fact,
that they get in the way of each other in a variety of situations,
and that is part of the reason why these ions merit interest
by aquarists. This article details the nature of strontium in
seawater, and it describes which marine organisms are known
to need strontium and for what purpose. It also describes which
marine organisms are known to take up strontium (such as corals),
whether they “need” it or not. Finally, it describes
how strontium is added, measured, and removed from marine aquaria.
Next month I hope
to extend these articles with an analysis of how much magnesium
and strontium are delivered to aquaria in limewater (kalkwasser).
My aquarium has not become depleted in strontium despite not
having added strontium supplements for several years. Combine
this practice with the fact that calcification is known to remove
strontium from solution, and one can only conclude that strontium
must be entering my aquarium in some way. Limewater seems the
most likely way, and I’ll report on such matters next
month.
Strontium
in Seawater
In full strength
seawater (S=35), strontium is present at approximately 90 μM
(μM is short for micromolar, which is a measure of the actual
number of ions present, as opposed to ppm (parts per million),
which is a measure of the mass of ions present). By concentration,
it is the fifth most abundant cation (positively charged ion)
behind sodium (Na+; 469,000 μM), magnesium (Mg++,
53,000 μM), calcium (Ca++;
10,300 μM), and potassium (K+; 10,200 μM).
In mass units, it is present in seawater at about 8 ppm.
The strontium concentration
is largely constant across the oceans, with local variations
of only 2-3% relative to calcium.4,
5 As salinity varies in lagoons and estuaries,
of course, the concentration of strontium rises and falls accordingly.
It was long thought that the strontium concentration was also
unchanged with depth,6 but more recent measurements
have shown that the strontium concentration rises somewhat with
depth due to the action of acantharians that deposit strontium
sulfate skeletons, slightly depleting the surface of strontium.
As these free floating organisms die and settle to the bottom,
the deeper waters become enriched in strontium as the skeletons
dissolve.4
Strontium, with
a molecular weight of 87.5 grams/mole is significantly heavier
than calcium (40 grams/mole) or magnesium (24.3 grams/mole).
In physical size, a strontium ion is about 13% larger than a
calcium ion, and 70% larger than a magnesium ion (Figure 1).
Figure
1
Comparison
of the size of various ions. Clockwise from the top left,
these are magnesium (Mg++), calcium (Ca++),
strontium (Sr++), carbonate (CO3--),
and sulfate (SO4--) ions.
Strontium is present
in seawater as the Sr++ ion,
meaning that it carries two positive charges, just as calcium
and magnesium do. Most of the strontium is present as the free
ion, with only water molecules attached to it.7 A
small portion (about 10%) of the strontium is present as a soluble
ion pair with sulfate (SrSO4), and much smaller portions
are paired with bicarbonate (SrHCO3+),
carbonate (SrCO3), fluoride (SrF+), borate
(SrB(OH)4+), and hydroxide (SrOH+).7
Habib Sekha (owner of Salifert) has suggested that strontium
in seawater may be ion paired to sulfate to a much greater degree
than suggested above, but I have not seen strong evidence to
support that hypothesis.
The average residence
time for a strontium ion in the ocean is on the order of 10-20
million years.7 That time is similar to magnesium
(20-50 million years) and is substantially longer than that
for calcium (a few million years) and aluminum (100 years).
It is also substantially less than sodium (about 250 million
years). In a certain sense, this is an indication of how reactive
strontium is: it stays in seawater a long time because it's
fairly unreactive, but it does get taken out of solution through
various biological and chemical processes more readily than
sodium does.
How does the reactivity
of strontium compare to calcium and magnesium? As mentioned
in the introduction, they are all very similar chemically. Size
is the primary difference, and that size difference actually
causes some chemical differences, especially the solubility
of certain strontium salts. Strontium carbonate (the primary
crystalline form of which is called strontianite) is less soluble
that calcium carbonate, which in turn is less soluble than magnesium
carbonate. In part, this may be the reason that strontium gets
into calcium carbonate skeletons of organisms, as is detailed
more below.
Interestingly, strontium
sulfate (also known as celestite) is much less soluble than
calcium sulfate and magnesium sulfate. While none of these are
actually saturated in seawater, strontium sulfate is close,
at 30% of saturation.8 That difference is important,
and in fact some organisms (such as the acantharians mentioned
above) use strontium sulfate as a skeleton (which is detailed
more below).
Organisms
That Use Strontium: Acantharia
One of the main
users of strontium in the ocean are the Acantharia.4,
9-16 These beautiful, free floating unicellular
microorganisms are related
to radiolaria. They have radiating spines of strontium sulfate
that are largely external to the central cytoplasm. Inside the
“body”, the spines are connected. The end result
is something that looks
like a microscopic sea urchin.
Acantharia live
in the upper regions of the oceans where they deposit their
strontium sulfate skeletons. Presumably, these skeletons are
protected from dissolution somehow, perhaps with an organic
coating as the radiolarian Sphaerozoum punctatum does,
described in the next section. When Acantharia die and sink,
the protection of the strontium sulfate is lost, exposing the
strontium sulfate to the open water, resulting in dissolution.
They are populous enough that they are an important part of
the strontium cycle in the oceans (which also includes river
and hydrothermal vent input), taking strontium from the surface
and delivering it to depths of up to 900 m, where most have
completely dissolved.14,15
Are there Acantharia
in reef aquaria? I don’t know. In aquaria that use natural
seawater they might be seeded into the aquarium every time there
is a water change. If there are appreciable numbers in some
aquaria, then they might well provide a significant sink for
strontium in those aquaria. In fact, they could cause rapid
depletion of strontium. In other aquaria, for example those
that use heavy skimming and artificial salt water, the likelihood
that they are present in important numbers is likely much smaller.
This potential difference between aquaria is one of many ways
that the strontium balance may vary between different aquaria.
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Organisms
That Use Strontium: Radiolaria
Certain species
of radiolaria also use strontium sulfate, despite having silica
skeletons. The radiolarian Sphaerozoum punctatum, for
example, release flagellated swarmers during reproduction which
contain crystals of strontium sulfate (celestite).17-19
These crystals are deposited inside a cytoplasmic vacuole, and
have a 50-100 nm thick coating of organic material on it. This
coating may reduce the likelihood of dissolution of the celestite,
and may be a clue as to how the Acantharia keep their strontium
sulfate spines from dissolving. What purpose these crystals
serve to the S. punctatum is unknown, but it may be
an antipredatory defense.
Organisms
That Use Strontium: Gastropods
Some gastropods,
such as the sea slug Aplysia
californica, have a clearly defined requirement for
strontium in the water. When they are grown in artificial seawater
lacking strontium, they develop deformed shells and statocysts
(that lack a statolith).20Statocysts
are balance organs in many invertebrates. They consist of a
fluid-filled sac containing statoliths that stimulate sensory
cells and help indicate position when the animal moves. Statoliths
themselves are small solid granules, and are made largely of
calcium carbonate in Aplysia
californica.
These organisms
are quite sensitive to reductions in strontium, with a drop
of only 1 ppm causing a detectable difference in development.
For this organism there is a critical window of strontium exposure
around day 4 of its life. Strontium added after that point cannot
make up for the poorly developed statolith, which causes erratic
swimming.
How exactly the
strontium is used in the deposition of shells and the statolith
is not known, but it is apparently somehow related to calcification.21
The statoliths of A. californica raised in normal seawater
have been shown to contain elevated strontium.22
In the absence of strontium, the calcification is decreased
by 80%. At low strontium levels, calcification was not significantly
reduced, but the shell and statolith were still defective. These
researchers concluded “Although the role of strontium
in embryonic calcification of A. californica remains
enigmatic, these data suggest that strontium affects a highly
discrete regulatory component because these more general indicators
of calcification and differentiation are unaffected by its absence.”
Organisms
That Use Strontium: Cephalopods
As in Aplysia
californica, strontium appears to be important to the development
of at least 7 species of cephalopod.23,24 In all
of these, the aragonite statolith develops properly in artificial
seawater containing 8 ppm strontium, but not in artificial seawater
from which strontium is absent. The end result for cephalopods
raised in seawater lacking strontium is uncontrolled swimming
due to the poor statolith development. For cuttlefish (Sepia
officinalis) the cuttlebone also develops improperly
in the absence of strontium.
Organisms
That Use Strontium: Corals and Calcerous Algae
Organisms that calcify
(that is, deposit calcium carbonate skeletons) are known to
incorporate strontium into them. This deposition may be:
Intentional for
positive reasons. That is, the strontium serves a useful purpose.
Perhaps the purpose is to initiate or maintain calcium carbonate
precipitation in some fashion. Some organisms described above
clearly fall into this category.
Intentional
for negative reasons. That is, the organism wants to get rid
of potentially toxic strontium and depositing it into a CaCO3
skeleton is one way to accomplish that task).
Accidental. That
is, the deposition of strontium serves no real purpose for
the organism, but is simply the result of the fact that strontium
looks rather like calcium, and gets into pathways intended
for calcium and becomes deposited into the skeleton. This
is obviously the way that strontium gets into abiotically
deposited calcium carbonate.
In the abiotic
precipitation of calcium carbonate from seawater (by the
slow addition of carbonate), strontium is incorporated into
the growing crystal at almost the same ratio to calcium that
is present in the seawater. That is, about 103:1, Ca:Sr (at
25 °C).25 Interestingly, he amount of strontium
incorporated is slightly lower at higher temperatures (105:1
at 30 °C), and slightly higher at lower temperatures (97:1
at 10 °C).13,25
This temperature
dependence has lead many researchers to investigate, and find
largely true, the idea that the strontium to calcium ratios
in corals might be used as a temperature probe for ocean temperatures.
Most interestingly, it has been extended into ancient coral
skeletons, where actual temperature measurements are lacking.26
Many factors have complicated these studies, such as
Different corals
incorporate different ratios at the same seawater temperature
and strontium levels,
The same corals
can deposit different ratios during the day and the night
Different parts
of the skeleton of a single coral may have different ratios
The presence
of zooxanthellae can significantly perturb the ratio.25
The incorporation
of strontium is strongly dependent on the strontium concentration
in solution (which may vary over geologic time, with depth,
and with salinity)
Other related measurements
(such as the incorporation of various oxygen isotopes into the
calcium carbonate) may ultimately turn out to be more useful
for temperature estimation. The ratio of the different strontium
isotopes (molecular weight 87 and 86) in deposits has also been
suggested to be a measure of the weathering of land, since the
ratio in rivers is different than in the ocean.27
In any case, there
are many fascinating studies reported related to strontium in
corals and other calcium carbonate deposits. While many of these
are only tangentially related to aquarium issues, some of the
basic issues are important for understanding the strontium balance
in aquaria.
In an old (1957)
study28 of 900 samples of calcium carbonate from
many different organisms, it was noted that:
“Analyses
of limestones, reef cores, limestone precursors, and fossils
indicate that replacement and recrystn. lower the Sr/Ca ratio”.
This fact is important because if calcium carbonate is the
ultimate basis for calcium additives to aquaria (such as CaCO3
in CaCO3/CO2 reactors, or CaCO3
heated to form lime that is later used to make limewater),
then the amount of strontium present in these ancient deposits
will control the amount getting into aquaria. If these deposits
are deficient in strontium, then an aquarium using them may
also become deficient.
“…
reef corals, and green aragonite algae all have high Sr/Ca
ratios that may be related to rapid deposition of carbonates
associated with photosynthesis processes”. Again, if
reef corals are not the ultimate source of CaCO3
used to make calcium supplements, then the levels in the aquarium
may drop over time, just as in (1).
“The Sr/Ca
ratio is characteristic of a species or a taxonomic group….”
In this case, if the organisms used to make the original CaCO3
are not the same species that are depositing CaCO3
in the aquarium, then the relative amount of strontium in
the supplement may be too high or too low, allowing the aquarium
to become enriched or depleted over time. The same could be
said for the deposition temperature.
Many recent studies
have shown the Ca:Sr ratio for many corals at typical tropical
reef temperatures and at normal seawater strontium concentrations
to be in the range of 100:1 to 120:1. When looked at very closely,
it has been noted that corals do actually seem to incorporate
slightly more strontium than happens abiotically under the same
temperature and ambient strontium conditions (about 103:1 (at
25 °C).25 Is that because the corals “want”
the strontium? Or just an artifact of the pathway
that corals use to get calcium deposited29 into
calcium carbonate? The answer is unknown, but there are a few
clues buried in other studies, and these are described below.
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Do Corals
Need Strontium?
Over the past decade,
a number of advanced aquarists have indicated that certain calcifying
corals in their aquaria have responded positively when they
have added strontium. Julian Sprung, for example, indicated
that in one of his aquaria, strontium boosted growth considerably.
Unfortunately, he does not report strontium levels from that
aquarium.1
The several possible
reasons for corals to take up strontium were presented earlier
in this article. These reasons range from needing strontium
for some purpose, through not caring one way or the other about
strontium, to depositing it only as a means of eliminating it
from their bodies. What does the scientific literature have
to say on this subject? Unfortunately, not enough. There has
never been a published study that showed exactly what happens
to the health of corals (as measured via calcification rates
or any other means) when strontium is absent.
There have been
numerous studies that have shown what happens when strontium
is raised above natural levels. In those studies, the amount
of strontium incorporated rises linearly with strontium concentration
up to at least 300 ppm in Stylophora
pistillata.30 It has also been shown that
calcium and strontium uptake may use the same pathways, since
they are both inhibited by the same organic molecules that block
certain protein transporters.30 Depending on the
conditions, calcification can increase on adding extra strontium,
as it does with added calcium.31,32 Nevertheless,
these studies say little about whether natural levels of strontium
are important for normal calcification.
Another study examined
in microscopic detail where the strontium is located in Galaxea
fascicularis.33 They found that strontium was
significantly enriched in the mucous layers. They propose that
the strontium is used to neutralize (thanks to its +2 charge)
the highly anionic (that is, negative charged) individual mucin
glycoproteins. Once neutralized, the mucin can condense into
functional mucin granules. These glycoproteins are highly sulfated,
and if one were selecting a cation to bind to and neutralize
the mucin, one might well select a divalent ion with a preference
for binding sulfate. That is exactly what strontium provides,
recalling the fact mentioned above that strontium sulfate is
much less soluble than either calcium or magnesium sulfate.
The authors also
go on the state that the mucin layer itself may play an important
role in ensuring that calcium is delivered to the ectodermal
cells. That is, it helps maintain an artificially high calcium
concentration near the surface of the ectodermal cells. This
process would help what is otherwise believed to be a limiting
factor in calcification: the active transport of calcium. Whether
this hypothesis is valid or not remains to be established. Nevertheless,
it has, for the first time, provided a plausible mechanism
for corals to benefit from strontium.
Toxicity
of Elevated Strontium
There have been
relatively few studies on the toxicity of elevated strontium
to most marine organisms. In most studies, researchers have
found strontium to not be very toxic at levels that might be
attained in a reef aquarium. In one study, researchers looked
at developing mussel embryos (Mytilus californianus)
for effects from barium and strontium. For strontium, they concluded
that there were no effects at environmentally relevant levels,
although barium was quite toxic at even fairly low levels.34
The table below
summarizes some of the toxicity data that is known for strontium
to wholly marine organisms (that is, those that do not spend
any part of their lives in freshwater where they might be more
sensitive to ionic toxins. For example, certain
freshwater organisms are killed by strontium at levels far
below those found in natural seawater). The most sensitive organism
in table 3 appears to be a crab, with 38 ppm strontium reported
to be lethal. If that experiment is valid, then aquarists would
be cautioned to keep strontium from rising much above natural
levels.
*
The LC50 is defined as the concentration at which 50% of
the organisms die in the specified time.
Strontium
in Marine Aquaria
In a study of 23 marine aquaria, Shimek37
showed that the strontium levels ranged from 4 to 10 ppm, with
a mean of 6.8 ppm. Some of these aquarists were likely adding
strontium supplements, and some not. My own aquarium, where
I have not added any strontium supplements in several years,
has a strontium level of 15 ppm (measured by ICP, a technique
describe later in this article). That 15 ppm strontium matches
my measured value for the Instant Ocean salt mix that I use.
What can be concluded
from this data? One obvious conclusion is that some aquaria
will maintain strontium levels in the absence of any specific
strontium supplements. That result may not apply to all aquaria,
however, for the various reasons given throughout this article.
Nevertheless, the strontium level in my aquarium is high enough
without supplements that I would not like to see it raised.
Consequently, I would not recommend that any aquarists add strontium
under the assumption that it is low, unless they have actually
determined that it is low.
One other comment
on strontium in marine aquaria: It has been claimed that strontium
is a poison, and was attributed by Shimek2,3 to be the likely causative factor in the deaths
of a wide variety corallimorpharians (mushrooms) in a reef aquarium
when the strontium level was raised over a two week period to
double natural levels. That certainly could have been the case,
but I do not believe that in general a strontium concentration
at 2X natural levels is toxic to typical corallimorpharians
that aquarists maintain. I have many different species in my
aquarium with 2X natural levels of strontium, and most grow
quite rapidly, some even being at the pest level. I’ve
never had one quickly die after adding it to my aquarium. Perhaps
the corallimorpharians that he is referring to actually died
from something else.
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Sources
of Strontium in Marine Aquaria
The original source
of strontium in aquaria is the artificial or natural seawater
used to set up the aquarium, and with which any water changes
are performed. Some artificial salt mixes have been reported
to be slightly
elevated in strontium (9-18 ppm)38 while others
had levels comparable to natural seawater (~ 8 ppm). None in
that study were deficient in strontium. My own analysis of artificial
seawater made using Instant Ocean at a salinity of S=35 showed
about 15 ppm (the previous study showed about 17 ppm). Based
on the toxicity data presented above, it would seem to be beneficial
for these salt mixes to as closely match 8 ppm as possible,
and not have elevated levels.
The other major
source is calcium supplements. Many of these supplements contain
strontium, either by “accident” (as in the case
of calcium carbonate with impurities of strontium carbonate
that is used in CaCO3/CO2 reactors) or
because strontium is intentionally added by manufacturers.
In the case of commercial
calcium supplements, some manufacturers add strontium to some
of them. Seachem, for example, adds strontium to Reef Complete
and Reef Advantage Calcium, but not to their other calcium products.
These two products contain a molar ratio of about 2185:1 (calcium
to strontium). As will be seen below by comparison to other
methods, that value is within the wide range of ratios provided
by typical media used in CaCO3/CO2 reactors.
How much is an optimal amount to add, however, is not entirely
clear, and this “problem” of matching the input
of strontium to the export is discussed in detail below. Other
manufacturers, such as Kent, do not add strontium to any of
their normal calcium-only supplements. Nevertheless, these supplements
will all contain some strontium. The question is how much.
In the case of limewater,
it is not apparent how much strontium is present. I hope in
the near future to report on how much strontium is present in
solid lime, in the clear limewater, and in the residue at the
bottom of a limewater reservoir.
Striking a perfect
balance between strontium input and export, even when using
a CaCO3/CO2 reactor, may require measurements
and adjustments. The argument that using ground up coral skeletons
in a CaCO3/CO2 reactor will supply exactly
what corals need is too simplistic. Different sources of calcium
carbonate have different amounts of strontium in them. In testing
of samples used by aquarists, Bingman39
reported a Ca: Sr ratio of 15,385:1 for Korlith and 7143:1 for
Super Calc Gold. Similarly, Hiller40
reported 2732:1 for a quarried limestone and 1379:1 for Nature's
Ocean brand crushed coral. These values are all FAR below the
amount of strontium taken out by calcification, which is more
typically like 110:1 for calcification by corals and 100:1 for
abiotic precipitation of aragonite (although the exact value
for each of these depends on the ambient strontium concentration,
the temperature, and the species involved).25 If
these reported values are actually real, and not in some way
an artifact of the testing procedures, then it would seem that
using such media would soon lead to depletion of strontium (in
the absence of strontium additives).
A different way
to get a handle on the strontium being added this way is to
look at how much strontium is added to aquaria each year using
these media. If one were adding 16 ppm of calcium (and necessarily
0.8 meq/L of alkalinity) every day for a year (the equivalent
of 2% of saturated limewater every day, but instead using these
media in a CaCO3/CO2 reactor), the following
species would be added to the water.
Table
2. Cumulative amount of calcium, magnesium, and strontium
added to a reef aquarium over the course of a year using
a CaCO3/CO2 reactor.
Conklin
Limestone
Nature's
Ocean
Koralith
Super
Calc Gold
Metal
Amount
added in 1 year (ppm)
Amount
added in 1 year (ppm)
Amount
added in 1 year (ppm)
Amount
added in 1 year (ppm)
Calcium
5957
5957
5957
5957
Magnesium
62
39
14
42
Strontium
5
9
0.8
1.5
From this table
it is clear that the amount of strontium added each year can
be significant compared to the natural level of 8 ppm, but it
does not have the same huge turnover that is present in calcium.
Consequently, the amount of strontium coming from other sources,
such as the salt mix itself, may actually dominate the additions.
Another potential
source of strontium is fish food. Strontium is present in many
such foods, but not enough to have a significant impact on typical
levels of strontium (~8 ppm). Table 2 shows some data from Shimek41
that have been recalculated to show the effect of adding 5 grams
of food per day to a 100-gallon aquarium for a year. The effect
on strontium of 0.01 - 0.7 ppm assumes that all of the strontium
goes into solution. Whether that actually happens or not is
moot as the total contribution to strontium is small. Also shown
in Table 3 are the same data for calcium, showing that some
foods could add a significant amount of calcium to reef aquaria.
Table
3: Calcium and Strontium in Aquarium Foods
Food
Calcium
Concentration(ppm)
Calcium
added to 100 gallon tank in 1 year(ppm in aquarium)
Strontium
Concentration (ppm)
Strontium
added to 100 gallon tank in 1 year (ppm in aquarium)
Formula One
800
4
12
0.06
Formula Two
1700
8
14
0.07
Prime Reef
860
4
11
0.05
Lancefish
4700
23
7
0.03
Silversides
4300
21
16
0.08
Brine Shrimp
140
1
2.3
0.01
Plankton
1700
8
28
0.14
Golden Pearls
8700
42
38
0.19
Gold Flakes
7200
35
39
0.19
Tahitian Blend
440
2
28
0.14
Saltwater Staple
17000
82
150
0.73
Nori
2400
12
25
0.12
Sinks for
Strontium in Marine Aquaria
The primary sink
for strontium in aquaria is coprecipitation with calcium carbonate.
This occurs in organisms and also during the abiotic (non-biologically
driven) precipitation of calcium carbonate (such as on heaters).
It is anticipated that strontium is removed at a rate of about
1 strontium atom for every 100 calcium atoms. How much does
this end up being?
Using the same assumptions
on calcification rates that were used for sources of strontium
above, we can make some ballpark estimates. If one caused the
deposition of 16 ppm of calcium (and necessarily 0.8 meq/L of
alkalinity) every day for a year (the equivalent of 2% of saturated
limewater every day), then at 100:1, the amount of strontium
removed in a year amounts to a whopping 127 ppm of strontium.
That amount
dwarfs the strontium inputs described above. How can
that be? Why doesn’t the strontium disappear in short
order (i.e., a month or less)? Why were the strontium levels
in tested aquaria no lower than 4 ppm? Even at 4 ppm Sr++,
the Ca:Sr deposition ratio should be on the order of 200:1,
since incorporation is approximately linearly related to the
Sr++ concentration. Could the
answer be water changes using salt mixes with adequate or elevated
strontium? That wouldn’t seem to supply enough at typical
change rates of 5-20% per month. Strontium supplements? Maybe.
Perhaps in the case of aquaria using limewater, the limewater
delivers enough strontium to balance this export. Perhaps in
aquaria, with organic levels higher than in seawater, much of
the strontium is bound to organics, reducing its availability
to corals? Perhaps the previously reported tests of strontium
levels in reactor media were flawed somehow. Perhaps my assumptions
are flawed somehow. I don’t presently know the answer(s).
Supplements
for Strontium in Marine Aquaria
There are a variety
of commercial supplements for strontium. I would use a pure
strontium supplement (sold by, for example, ESV,
Seachem,
Kent,
and Warner),
as opposed one that is tied to other ions that may have no relationship
to the need for strontium. I also would not use one unless the
aquarium was determined to be low in strontium.
Measuring
Strontium in Marine Aquaria
There are two primary
ways to test for strontium in aquaria. The first is to use one
of the two commercial test kits available. These are made by
Seachem
and Salifert.
Both are complicated tests, which is not surprising as it is
difficult to measure strontium against a large background of
chemically similar calcium and magnesium. I’ve not used
either of these kits for several years, and have not used the
current version sold. I hope to review the current commercial
kits in the future.
A second way to
measure strontium is to use the type of equipment available
in commercial
analytical laboratories, such as ICP (inductively coupled
plasma) and ICP-MS (inductively coupled plasma-mass spectrometry).
In ICP, the water sample is sent into a very hot plasma. The
individual ions then emit light because they are so very hot.
ICP is very sensitive to strontium (quantifiable down to about
0.002 ppm) due to a very strong emission from strontium at 408
nm. I have used ICP myself to quantify strontium in my aquarium
(15 ppm) and in the Instant Ocean salt mix that I use (also
15 ppm).
Proud
sponsor of this column
Recommendations
for Strontium
My recommendation
is to maintain strontium in reef aquaria at something approaching
natural levels. There is no evidence that strontium at these
levels in detrimental to any marine organism (although it might
be). There is strong scientific evidence that some organisms
need strontium, albeit not the organisms that most reef keepers
maintain. Finally, there is anecdotal evidence from a number
of advanced aquarists that depleted strontium is detrimental
to the growth of corals that many aquarists maintain.
How is one to maintain
natural levels? That, of course, necessitates a suitable test
for strontium. Perhaps the test kits are suitable for this purpose.
If not, sending a sample out to a lab might be a reasonable
alternative for some aquarists. If the result comes back in
the 6-15 ppm range, there is not likely any action that needs
to be taken. If the level is higher than 15 ppm, reducing the
strontium levels via water changes with a suitable salt mix
may be the best method. If strontium levels are below 6 ppm,
adding a strontium supplement may be in order.
Remember: in my
aquarium without any recent strontium additions, strontium was
already elevated above natural levels. I would not like to see
it get any higher. Consequently, adding a supplement in the
absence of knowing the strontium levels is not advisable.
Happy Reefing!
References
1 The Reef
Aquarium: A Comprehensive Guide to the Identification and Care
of Tropical Marine Invertebrates (Volume 1) J. Charles
Delbeek, Julian Sprung Two Little Fishies; (July 1994).
4. Seawater
strontium and Sr/Ca variability in the Atlantic and Pacific
oceans. de Villiers, S. Department of Geological Sciences,
University of Washington, Seattle, WA, USA. Earth and Planetary
Science Letters (1999), 171(4), 623-634.
5. Barium
and strontium concentrations in Pacific and Mediterranean seawater
profiles by direct isotope dilution mass spectrometry.
Bernat, Michel; Church, Thomas; Allegre, Claude J. Inst. Phys.
Globe, Univ. Paris IV, Paris, Fr. Earth and Planetary Science
Letters (1972), 16(1), 75-80.
6. Strontium
concentrations and strontium-chlorinity ratios in seawater of
the North Pacific and the adjacent seas of Japan. Nagaya,
Yutaka; Nakamura, Kiyoshi; Saiki, Masamichi. Dep. Environ. Contam.,
Natl. Inst. Radiol. Sci., Japan. Journal of the Oceanographical
Society of Japan (1971), 27(1), 20-6.
7. Chemical
Oceanography, Second Edition. Millero, Frank J.; Editor.
USA. (1996), 496 pp. Publisher: (CRC, Boca Raton, Fla.)
8. Marine
barite and celestite saturation in seawater. Rushdi,
A. I.; McManus, J.; Collier, R. W. College of Oceanic and Atmospheric
Science, Oregon State University, Corvallis, OR, USA. Marine
Chemistry (2000), 69(1-2), 19-31.
9. Trace
elements in acantharian skeletons. Brass, G. W. Rosenstiel
Sch. Mar. Atmos. Sci., Univ. Miami, Miami, FL, USA. Limnology
and Oceanography (1980), 25(1), 146-9.
10. Morphologies
and transformations of celestite in seawater: the role of acantharians
in strontium and barium geochemistry. Bernstein, Renate
E.; Byrne, Robert H.; Betzer, Peter R.; Greco, Anthony M. Dep.
Mar. Sci., Univ. South Florida, St. Petersburg, FL, USA. Geochimica
et Cosmochimica Acta (1992), 56(8), 3273-9.
11. General
characteristics and radioecology of the strontium Radiolaria
organisms Acantharia. Strontium-87 and strontium-90
in Acantharia. Reshetnyak, V. V. USSR. Editor(s): Polikarpov,
G. G. Khemoradioekologiya Pelagiali Bentali (1974), 188-91,
259-70. Publisher: "Naukova Dumka", Kiev, USSR
12. Marine
celestite and the role of acantharians in oceanic strontium
and barium geochemistry. Bernstein, Renate Ellen. Univ.
of South Florida, Tampa, FL, USA. Avail. UMI, Order No. DA3001934.
(2000), 125 pp. From: Diss. Abstr. Int., B 2001, 62(1), 117.
13. Coprecipitation
of cations with calcium carbonate. Coprecipitation of strontium(II)
with aragonite between 16 and 96.deg. Kinsman, David
J. J.; Holland, Heinrich D.. Princeton Univ., Princeton, NJ,
USA. Geochimica et Cosmochimica Acta (1969), 33(1), 1-17.
14. Strontium
distribution in Geosecs oceanic profiles. Brass, Garrett
W.; Turekian, Karl K. Dep. Geol. Geophys., Yale Univ., New Haven,
CT, USA. Earth and Planetary Science Letters (1974), 23(1),
141-8.
15. Acantharian
fluxes and strontium to chlorinity ratios in the North Pacific
Ocean. Bernstein, R. E.; Betzer, P. R.; Feely, R. A.;
Byrne, R. H.; Lamb, M. F.; Michaels, A. F. Dep. Mar. Sci., Univ.
South Florida, St. Petersburg, FL, USA. Science (Washington,
DC, United States) (1987), 237(4821), 1490-4.
16. Comparative
analysis of vertical distribution patterns of epipelagic radiolaria,
chlorophyll, and zooplankton in different regions of he North
Atlantic Ocean (June-Sept. 2001). Zasko, D. N.; Vedernikov,
V. I. Inst. Okeanol. im. P. P. Shirshova, RAN, Moscow, Russia.
Okeanologiya (Moscow, Russian Federation) (2003), 43(1), 69-77.
17. Biological
minerals formed from strontium and barium sulfates. III. The
morphology and crystallography of strontium sulfate crystals
from the colonial radiolarian, Sphaerozoum punctatum.
Hughes, N. P.; Perry, C. C.; Anderson, O. R.; Williams, R. J.
P. Inorg. Chem. Lab., Univ. Oxford, Oxford, UK. Proceedings
of the Royal Society of London, Series B: Biological Sciences
(1989), 238(1292), 223-33, 3 plates.
18. Macromolecular
assemblages in controlled biomineralization. Perry,
C. C.; Fraser, M. A.; Hughes, N. P. Chem. Dep., Brunel Univ.,
Uxbridge/Middlesex, UK. ACS Symposium Series (1991), 444(Surf.
React. Pept. Polym.: Discovery Commer.), 316-39.
19. Transmission
and scanning electron microscopic evidence for cytoplasmic deposition
of strontium sulfate crystals in colonial radiolaria.
Anderson, O. R.; Perry, C. C.; Hughes, N. P. Lamont-Doherty
Geol. Obs., Columbia Univ., Palisades, NY, USA. Philosophical
Transactions of the Royal Society of London, Series B: Biological
Sciences (1990), 329(1252), 81-6.
20. Effects
of strontium on the embryonic development of Aplysia californica.
Bidwell, Joseph P.; Paige, John A.; Kuzirian, Alan M. Howard
Hughes Med. Inst., Woods Hole, MA, USA. Biological Bulletin
(Woods Hole, MA, United States) (1986), 170(1), 75-901
21. The
effect of strontium on embryonic calcification of Aplysia
californica. Bidwell, Joseph P.; Kuzirian, Alan;
Jones, Glenn; Nadeau, Lloyd; Garland, Lisa. Howard Hughes Med.
Inst., Woods Hole Oceanogr. Inst., Woods Hole, MA, USA. Biological
Bulletin (Woods Hole, MA, United States) (1990), 178(3), 231-8.
22. Statoconia
formation in molluscan statocysts. Wiederhold M L;
Sheridan C E; Smith N K Division of Otorhinolaryngology, The
University of Texas Health Science Center at San Antonio, USA
SCANNING ELECTRON MICROSCOPY (1986), 2 781-92.
23. Strontium
is required for statolith development and thus normal swimming
behavior of hatchling cephalopods. Hanlon, Roger T.;
Bidwell, Joseph P.; Tait, Richard. Mar. Biomed. Inst., Univ.
Texas Med. Branch, Galveston, TX, USA. Journal of Experimental
Biology (1989), 141 187-95.
24. Growth
increments and biomineralization process in cephalopod statoliths.
Bettencourt, Vera; Guerra, Angel. Instituto de Investigaciones
Marinas (CSIC), Vigo, Spain. Journal of Experimental Marine
Biology and Ecology (2000), 248(2), 191-205.
25 The effect
of algal symbionts on the accuracy of Sr/Ca paleotemperatures
from coral. Cohen, Anne L.; Owens, Kathryn E.; Layne,
Graham D.; Shimizu, Nobumichi. Department of Geology and Geophysics,
Woods Hole Oceanographic Institution (WHOI), Woods Hole, MA,
USA. Science (Washington, DC, United States) (2002), 296(5566),
331-334.
26. An assessment
of the Sr/Ca ratio in shallow water hermatypic corals as a proxy
for sea surface temperature. Marshall, John F.; McCulloch,
Malcolm T. Research School of Earth Sciences, Australian National
University, Canberra, Australia. Geochimica et Cosmochimica
Acta (2002), 66(18), 3263-3280.
27. Causes
of changes in seawater 87Sr/86Sr from the study of Sr isotopes
of loess from Chinese loess plateau. Su, Xiao-Yun;
Yang, Jie-Dong; Chen, Jun. Department of Earth Sciences, Nanjing
University, Nanjing, Peop. Rep. China. Nanjing Daxue Xuebao,
Ziran Kexue (2003), 39(3), 327-336.
28. Biogeochemical
deposition of strontium. Odum, Howard T. Publs. Inst.
Marine Sci. (1957), 4(No. 2), 38-114. From: Biol. Abstr. 33,
Abstr. No. 530 (1959).
30. Kinetics
of strontium uptake in the scleractinian coral Stylophora
pistillata. Ferrier-Pages, Christine; Boisson,
Florence; Allemand, Denis; Tambutte, Eric. Centre Scientifique
de Monaco, Monaco, Monaco. Marine Ecology: Progress Series (2002),
245 93-100.
31. The
strontium, magnesium and sodium composition of Recent scleractinian
coral skeletons as standards for palaeoenvironmental analysis.
Swart, Peter K.. King's Coll., Univ. London, London, UK. Palaeogeography,
Palaeoclimatology, Palaeoecology (1981), 34(1-2), 115-36.
32. The
effect of seawater chemistry on the growth of some scleractinian
corals. Swart, Peter. King's Coll., Univ. London, London,
UK. Editor(s): Tardent, Pierre; Tardent, Ruth. Dev. Cell. Biol.
Coelenterates, Proc. Int. Coelenterate Conf., 4th (1980), Meeting
Date 1979, 203-8.
33. Low
temperature x-ray microanalysis of calcium in a scleractinian
coral: evidence of active transport mechanisms. Clode,
Peta L.; Marshall, Alan T. Analytical Electron Microscopy Laboratory,
Department of Zoology, La Trobe University, Melbourne, Victoria,
Australia. Journal of Experimental Biology (2002), 205(22),
3543-3552.
34. Developmental
effects of barium exposure in a marine bivalve (Mytilus
californianus). Spangenberg, Jill V.; Cherr, Gary
N. Bodega Marine Lab., Univ. California, Davis, CA, USA. Environmental
Toxicology and Chemistry (1996), 15(10), 1769-1774.
35. Experimental
study on the acute toxicity of cobalt, antimony, strontium and
silver salts in some Crustacea and their larvae and in some
Teleostei. Amiard, J. C.. Dep. Prot., CEA, St.-Paul-lez-Durance,
Fr. Revue Internationale d'Oceanographie Medicale (1976), 43
79-95.
36. Phototactic
variations in crustacean larvae due to diverse metallic pollutants,
demonstrated by a sublethal toxicity test. Amiard,
J. C.. Dep. Prot., Commis. Energ. At., Fontenay aux Roses, Fr.
Marine Biology (Berlin, Germany) (1976), 34(3), 239-45.