1.1 Source Water -
City Mains Water Is Not Good Enough
1.1.1 Background
* U.S. EPA requirements for water quality from municipal sources are insufficiently
pure for reef tank usage. For instance, the EPA standard for Nitrate (as NO3-N) is 10.0
mg/l, over twice the recommended maximum level. Extremely toxic (to inverts) heavy metals
such as copper are allowed at levels as high as 1 mg/l. Most public water supplies
have contaminants well below the EPA levels and some reef tanks have done fine on some
public supplies.
In general, however, it is recommended that some form of post processing be performed
on public water before it is introduced into the reef tank.
Although some people have access to distilled, de-ionized or reverse osmosis water from
public sources, most will use a home sized system to produce their tank water. The two
most common systems used are de-ionization resins, and reverse osmosis membranes.
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1.1.2 DI filters
De-ionization (DI) units come in two basic varieties: mixed bed and separate bed. Two
chambers are used in separate bed units, one for anion resins (to filter negatively
charged ions), the other for cation resins (to filter positively charged ions). Mixed bed
units use a single chamber with a mix of anion and cation resins.
DI units are 100% water efficient with no waste water. They are typically rated in
terms of grains of capacity (a grain is 0.065 grams). Once the capacity of the unit is
reached it either needs to be replaced or recharged (using strong acids and bases).
Recharging is normally only an option for separate bed units. A quick check of the
local water quality reports (normally available free from the water supply company) will
reveal the water purification capacity of a given DI unit. For example, if a unit rated at
1000 grains is purchased and the local water supply has a hardness of 123 mg/l (Missouri
River, USA), then the unit capacity is (1000*0.065)/0.123 = 528 liters = 139.5 gallons of
purified water.
Water production rates for DI units varies, but is typically around 10-15 gallons/hour.
Note that some contaminants captured by a DI unit may "break through"
long before the unit indicates its capacity has been reached. Silica is a classic example.
What happens is that silica is loosely bound to the resins initially, but is
replaced by stronger binding materials like carbonates as the resins become exhausted.
The use of two DI units in tandem, as mentioned elsewhere in this FAQ, helps to
eliminate this problem.
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1.1.3 RO Filters
Reverse osmosis (RO) units are normally based upon one of two membrane technologies:
cellulose triacetate (CTA) and thin film composite (TFC). CTA based systems are typically
cheaper and do not filter as well (90-95% rejection rates). TFC based systems cost more
but have higher pollutant rejection rates (95%-98%).
CTA membranes break down over time due to bacterial attack whereas TFC membranes are
more or less impervious to this. CTA units are not recommended for reef tank purposes.
TFC membranes are very sensitive chemically to the chlorine found in most water supplies.
It is therefore very important to regularly replace the carbon block pre-filter
associated with all better-grade TFC systems. TFC membranes are damaged by chlorine so a
properly functioning GAC prefilter is mandatory.
RO filters work by forcing water under pressure against the membrane. The membrane
allows the small water molecules to pass through while rejecting most of the larger
contaminants. RO units waste a lot of water. The membrane usually has 4-6 times as
much water passing by it as it allows though. Unfortunately, the more water wasted, the
better the membrane usually is at rejecting pollutants. Also, higher waste water flows are
usually associated with longer membrane life. What this means in practice is that 300
gallons of total water may be required to produce 50 gallons of purified water.
Like any filter, RO membranes will eventually clog and need to be replaced. Replacement
membranes cost around $50-$100. Prefilters are often placed in front of the membrane to
help lengthen the lifetime. These filters commonly consist of a micron sediment filter and
a carbon block filter. The micron filter removes large particles and the carbon filter
removes chlorine, large organic molecules and some heavy metals. Of course, the use of
prefilters makes initial unit cost more expensive but they should pay for themselves in
longer membrane life.
RO units are rated in terms of gallons per day of output with 10-50 gallon/day units
typically available. Note that the waste water produced by a RO unit is fine for hard
water loving freshwater fish such as Rift Lake cichlids. Some route the reject water to
the family garden.
The Spectapure brand of RO units has a good reputation.
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1.1.4 Further Comments About Water
The ultimate in home water purification comes from combining the two technologies and
processing the water from an RO unit though a DI unit. If a very high grade DI unit is
used, water equivalent to triple distillation purification levels can be achieved. Since
the water entering the DI unit can be 50 times purer than tapwater, the DI unit can
process 50 times as much before the resins are exhausted. This significantly reduces the
replacement or recharging cost of the DI unit. Using two DI units in tandem, moving the
2nd in as a replacement for an exhausted 1st unit, and replacing the 2nd unit with a new
unit will insure that no undesirable elements "break through" the exhausted 1st
unit and enter your supply.
If only one filter can be afforded, and waste water is not a concern, then it is
recommended that a TFC RO unit with pre-filters be purchased. If waste water is a
concern, or if only a small quantity of make-up water will be required (say, for a single
20 gallon tank), then a DI unit would be the preferred choice.
City water is unstable. Many cities modify their treatment process several times a
year, dramatically changing its suitability for reef usage. For instance, Portland has
great reef water - most, but not all, of the year.
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1.2 Additives
Calcium (Ca) - required addition. A range of 400-450 ppm Ca++ (10-11
mM) is recommended. The preferred method is the usage of Kalkwasser (Limewater) for all
evaporation make-up water. The use of Calcium Chloride (CaCl2) is known to cause problems
with alkalinity (provable by balancing the relevant chemical reactions occurring
in the
tank when CaCl2 is added) and contributes to a shift in the ionic balance of the water
which must be corrected via water changes. Still, CaCl2 is occasionally useful to repair
serious Ca++ deficits.
Calcium Carbonate - The use of Calcium Carbonate reactors is growing
in popularity as a replacement, or sometimes in addition to, Kalkwasser usage. Such
reactors use CO2 recirculated through a bed of calcium carbonate (typically crushed coral
like Geo-Marine) to reduce the pH and dissolve the calcium carbonate. A small fraction of
the recirculated water is allowed to re-enter the aquarium and is replaced in the reactor
with fresh tank water on a continuous basis. These systems are considerably more
mechanically complex than Kalkwasser systems, often involving CO2 tanks, electrical
valves, pH controllers, bubble counters, circulation pumps and related equipment. Once
setup and tuned for the calcium demand in a tank, they can often be left alone for months.
This low maintenance requirement is a primary benefit of the system, combined with the
potential to inject more calcium into the system than kalkwasser alone could do due to
kalkwasser's low solubility in make-up water. Note that calcium reactors may add residual
CO2 to the system which can fuel algae growth. This extra dissolved CO2 may be purged by
either enhanced gas exchange or by adding a small amount of kalkwasser to scavenge
the CO2. Newer reactors often have a second carbonate stage to process and utilize this
extra CO2. The efficiency of such a second stage is unknown to this author.
Two Part Calcium Solutions (CaCl2) - A third approach to calcium
addition is the use of the newly available two-part ionically balanced solutions. These
solutions use CaCl2 as a calcium source, but combine that material via the 2nd part
solution with complex ion formulas that negate the normal problems associated with CaCl2
usage. These two-part solutions are relatively expensive for large aquariums but may be
cost-effective for smaller tanks relative to the capital required for a calcium carbonate
reactor. Others simply find their usage more convenient than the other alternatives. These
additives will slowly raise the salinity of the water as a side effect. As always, monitor
and correct your salinity as necessary.
Chelated calcium - The efficacy of chelated calcium products available
for reef aquaria is questionable. To the best of our knowledge, there exists no scientific
evidence indicating that chelated calcium is especially available to corals and other
CaCO3 depositing invertebrates. Nothing is known about the uptake of chelated calcium
products by coral. And most importantly, there exists no evidence showing that chelated
calcium products support stony coral growth rates in excess of, or even *comparable to*
growth rates documented in aquaria where calcium is supplied as aqueous Ca(OH)2
[kalkwasser.]
Chelated calcium products also interfere with the ability to measure actual calcium
levels in the aquarium. In particular, chelated calcium cannot be measured by any kit
which uses EDTA titration, including the highly recommended HACH kit. Until such a
time as vendors supplying chelated calcium products make available well conceived,
carefully documented uptake and growth studies with their products, or the same
experiments are performed and published by third parties, we regard the use of chelated
calcium products in the reef aquarium to be experimental at best, especially when
kalkwasser and other non-chelated calcium sources are KNOWN to us to support the growth
and even reproduction of stony corals in the home aquarium.
Iodine () - SeaChem and Salifert have recently introduced test kits
which are finally allowing a view of actual usage in a reef tank. Note that iodine is
naturally present in ocean water at relatively low levels (around 0.06 ppm - yes that 60
parts per BILLION). It is currently considered important for both soft coral growth
and hard coral health. It is removed via skimming, activated carbon usage, and
assimilation into biomass. It may also be removed by unidentified processes like
precipitation.
Strontium (Sr) - used rapidly by most hard corals (weekly additions
usually performed). Test kits are becoming available but the accuracy of current kits is
still questionable. Natural ocean water levels of strontium is around 8 ppm.
Buffers - increase alkalinity and control pH. Desired range is 2.5-3.5
meq/L (7-10 dKH) alkalinity. Alkalinity can be raised by the addition of one of many
commercial buffer compounds. The addition of kalkwasser (saturated Ca(OH)2 solution - also
known as "limewater"), which is often done to maintain calcium levels, will help
maintain the alkalinity level. SeaChem's Marine Buffer, Reef Builder and Kent's
Superbuffer dKH are popular. The Coralife and Thiel buffer products have had less
favorable reviews.
Iron (Fe) - Used by alga. Add this if you want good macroalgae growth.
Be sure that macroalgae growth is favored or else plague levels of hair algae may result.
Copper (Cu) - Used as a medication in fish-only tanks. Copper is
highly toxic to invertebrates, even in very small concentrations. DO NOT USE THIS,
IN ANY FORM, EVER, IN A REEF TANK OR ANY TANK WHICH CONTAINS INVERTEBRATES. PERIOD!
Other additives, especially the commercial "secret formula" mixtures, are
more controversial. Some people report good results from some of them other people report
disaster or no effect.
Experiment cautiously with them if desired. We recommend that all products that refuse
to reveal what's in them be used with a great deal of caution.
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1.3 Testable Parameters
Note: parts per million (ppm) and milligrams per liter (mg/l) are virtually identical
in seawater and the units are used synonymously in this document.
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1.3.1 Alkalinity
Alkalinity is a measure of the acid buffering capacity of a solution. That is, it
is a measure of the ability of a solution to resist a decrease in pH when acids are added.
Since acids are normally produced by the biological action of the reef tank contents,
alkalinity in a closed system has a natural tendency to go down. Additives are used to
keep it at a proper level.
Correct alkalinity levels allow hard corals and coralline algae to properly secrete new
skeletal material. When alkalinity levels drop, the carbonate ions needed are not
available and the process slows or stops.
Alkalinity is measured in one of three units: milliequivalents per liter (meq/l),
German degrees of hardness (dKH) or parts per million of calcium carbonate (ppm CaCO3).
Any of the units may be employed but dKH is most commonly used in the aquarium hobby and
meq/l is used exclusively in modern scientific literature. The conversion for the three
units is: 1 meq/l = 2.8 dKH = 50 ppm CaCO3 [As an aside, there is an imperial unit
of alkalinity and hardness which is 'grains per gallon'. The water softening industry uses
this unit. 1 gpg = 17 ppm CaCO3.]
A word of caution about the ppm CaCO3 unit is in order. The 'ppm CaCO3' unit reports
the concentration of CaCO3 in pure water that would provide the same buffering capacity as
the water sample in question. This does not mean the sample contains that much CaCO3.
In fact, it tells you nothing about how much of the buffering is due to carbonates,
it is only a measure of equivalency.
Alkalinity is often confused with carbonate hardness since both participate in acid
neutralization and test kits may express both in either of the three units. However,
carbonate hardness is technically a measure of only the carbonate species in equilibria
whereas alkalinity measures the total acid binding ions present which may include
sulfates, hydroxides, borates and others in addition to carbonates. In natural seawater,
though, carbonates make up 96% of the alkalinity so equating alkalinity with carbonate
hardness isn't too far off. As long as you're using a salt mix which yields an ion mix
close to that of Natural Sea Water (NSW) you can also make this assumption. Some salt
manufacturers alter the alkalinity component of their mix to increase the percentage of
borates to (bi)carbonates in order to maintain a stabler pH in the aquarium. We do not
feel this is good, and highly recommend you watch the trade magizines for reports on
borates in salt mixes. (OK, OK, here's a preview... Instant Ocean does NOT have
abnormal borates based on initial testing.)
Recommended values for alkalinity vary depending on who's work you read. Natural
surface seawater has an alkalinity of about 2.4 meq/l. Following are levels recommended by
various authors.
From John Tullock (1991) "The Reef Tank Owner's Manual": page 46 - Alkalinity
range should be 3.5 to 5.0 meq/l. page 94 - Alkalinity reading of 2.5-5.0 meq/l is
proper. page 188- Alkalinity should be about 3.5 meq/l. (In reference to maintaining
Tridacna clams.)
From Albert Thiel (1989), in "Small Reef Aquarium Basics" recommends
5.35-6.45 meq/l. This is an artificially high level which may initiate a
"snowstorm" of CaCO3 precipitate. Most reef aquarists do not believe in such
extreme and unnatural levels and recommend 3.0-3.5 meq/l as a good range instead.
The chemistry of how alkalinity, pH, CO2, carbonate, bicarbonate, and other ions
interrelate is fairly complex and is beyond the scope and detail of this document.
Some recommended test kits for alkalinity are the SeaTest kit, the inexpensive Tetra kit
and the LaMotte kit. The SeaTest kit measures in division of 0.5 meq/l or, if the amount
of solution is doubled, 0.25 meq/l. The SeaTest kit uses titration in which the acid and
indicator are included in the same reagent. The LaMotte kit is a little more expensive,
though still fairly cheap, and is somewhat more accurate. The unit of titration is
4 ppm CaCO3 although in practice, one drop from the titration tube may be up to twice this
amount making the resolution about 0.15 meq/l. The Lamotte kit has a separate indicator
tablet and acid reagent which is a nice feature.
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1.3.2 Calcium
Calcium content is referred to as 'calcium hardness' and is measured either in parts
per million of calcium ion (ppm Ca++) or parts per million equivalent calcium carbonate
(ppm CaCO3). Calcium hardness is often confused with alkalinity and carbonate
hardness since the 'ppm CaCO3' unit may be used for all three. As with alkalinity, a
calcium level expressed as X ppm CaCO3 does not imply that X ppm of calcium carbonate is
present in the tank; it merely states that the sample contains an equivalent amount of
calcium as if X ppm of CaCO3 were added to pure water. The reading also does not tell you
how much carbonate is present. Calcium hardness test kits are different from
alkalinity kits.
Some people have reported difficulties with the LaMotte calcium hardness kit. The Hach
'Total Hardness and Calcium' kit has not had these reports. Both express results in ppm
CaCO3. The relationship between CaCO3 and Ca++ is:
1 ppm CaCO3 = 0.4 ppm Ca++
The results from a test kit reading in ppm CaCO3 may be converted to the molar
concentration scale by dividing by 100.
100 ppm CaCO3 = 1 mM Ca++
40 ppm Ca++ = 1 mM Ca++
Calcium levels of natural surface seawater are around 420 ppm Ca++ (10.5 mM). In a well
running reef tank you will notice, sometimes dramatic, calcium depletion. Calcium addition
in some form is essential. A calcium level above 400 ppm is required and a range of
400-450 ppm Ca++ is recommended. Most reefkeeping books (see bibliography) explain the
options for calcium addition.
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1.3.3 pH
The suggested reef tank range is 8.3 to 8.4. The pH should hold its own unless
alkalinity is low. If alkalinity is OK but pH is low there is probably a buildup of
organic acids or a serious lack of gas exchange resulting in the retention/accumulation of
CO2 which lowers pH.
Note that it is perfectly normal for the pH of a tank to swing considerably. There is a
daily pH cycle where the pH is lowest just after the end of the dark period and highest
sometime before the end of the light period. Having a pH range from 7.9 to 8.4 is not
unheard of. Larger swings are probably indicative of low buffer levels or poor gas
exchange.
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1.3.4 Nitrate (NO3)
Two units are used to measure nitrates: nitrate (NO3-) and nitrate nitrogen (NO3-N or
just N). The ratio is:
1 ppm NO3-N = 4.4 ppm NO3-.
Nitrates themselves may not be a problem but serve as an easily measured indicator of
general water quality. Many hard to test for compounds like dissolved organics tend to
have levels that correlate well with nitrate levels in typical tanks.
Different authors cite varying upper nitrate values permissible. No higher than 5 ppm
NO3- is a good number with less than 0.25 ppm recommended. Unpolluted seawater has nitrate
values below detectable levels of hobbyist test kits, so "unmeasurable" is the
goal to strive for.
Most test kits measure nitrate-nitrogen. Do not forget to multiply by 4.4 to get the
ionic nitrate reading. LaMotte makes a nitrate test kit that will measure down to 0.25 ppm
NO3-N. The Hach kit, which measures down to 0.02 ppm N03-N has basic chemistry
problems in saltwater and is no longer recommended.
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1.3.5 Phosphate (PO4)
Phosphates, along with nitrates, are a primary nutrient of algae. Tanks with
"high" levels of phosphates tend to be infested with hair algae. All authors
cite zero ppm PO4 as a good goal. An upper level 0.1 ppm is recommended by Tullock (1991)
with less than 0.05 ppm given by Thiel (1991).
The use of kalkwasser has been closely tied with reduction in phosphate levels. This
may be due to precipitation of the phosphates at the kalkwasser injection site, or, more
likely, due to increased export via skimming due to the associated higher system pH.
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1.3.6 Specific Gravity
Short form:
Specific Gravity is temperature dependant. See the next table for a quick lookup of the
recommended hydrometer readings. They are based upon our recommended S.G. of 1.025 at 60
degrees F.
Degrees F. Hydrometer reading.
50 1.0255
55 1.0252
60 1.0250
65 1.0246
70 1.0240
75 1.0233
80 1.0226
85 1.0218 (rather hot for most tanks)
90 1.0210 (very hot for most tanks)
In more detail:
1.025 recommended for reef tanks. Note that virtually all hydrometers are calibrated
for measurements at a temperature of 60 F. Included below is a short table of temperature
adjustments. Add the value shown to your hydrometer reading to get an accurate reading.
Degrees F. Correction
50 -0.0005
55 -0.0002
60 0.0000
65 0.0004
70 0.0010
75 0.0017
80 0.0024
85 0.0032
90 0.0040
For example: If the hydrometer reads 1.0235 at 80F, the actual Specific Gravity is
1.0235 + 0.0024 = 1.0259
Note: If your tank is between 75F and 80F, this means you should try and keep your
Specific Gravity around 1.0230 to 1.0235.
For all practical purposes, the scale is linear between data points, so you can simply
extrapolate between table entries. For instance, 78F is 3/5 the distance between 75F and
80F; the difference in corrections is 0.0024-0.0017 = 0.0007. 3/5th of 0.0007 is 0.0004.
Add the offset 0.0004 to the base value for 75F of 0.0017 and you get a correction value
for 78F of 0.0021.
It is fairly common in the literature to see references to salinity in terms of Parts
Per Thousand (PPT). For salinities in the range we are interested in, the conversion
formulas are:
Salinity = 1.1 + 1300 * (Temperature corrected Specific Gravity - 0.999)
Temperature corrected Specific Gravity = ((Salinity - 1.1) / 1300) + 0.999;
Here is a short table of some common values:
Salinity Specific Gravity
20 PPT 1.0135
25 PPT 1.0174
30 PPT 1.0212
35 PPT 1.0251 * Typical Ocean Value *
40 PPT 1.0289
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1.4 Water Changes
"The solution to pollution is dilution". Water changes are used to correct
problems. Minimal changes of 5%/year when all is set up and running smoothly may suffice.
Some feel that an occasional water change of about 20% every 1-3 month is a reasonable
safety net that may help prevent contaminant buildup, shift in ion balance, and trace
element depletion problems. Others recommend 5%-10% per week.
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