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Reef Aquarium Chemistry Maintenance
By Carl Strohmeyer-PAMR 38+ years experience
Calcium is an essential element required by our reef aquarium. It is the building block for many hard corals, but is still required by all reef inhabitants, even fish! Your reef aquarium calcium level should be 400-450 ppm.
Since fish in marine environments constantly drink the water around them, they have a chemistry that is in sync with their environment.
A regular dosing/supply of calcium also supplies essential mineral Cations that again all reef inhabitants require.
Use of popular Calcium Chloride Dehydrate products only or along with economy Soda Ash Sodium Carbonate products sold by discount bulk suppliers can result in a slow build up of sodium chloride even with a stable specific gravity or salinity, resulting in less than optimal ionic balance for your reef aquarium. This over time is generally difficult to measure by marine/reef keepers, with the result of marine aquarium keepers potentially looking in to incorrect reasons for declining results (such as lighting).
This is where the 3 step AAP Balling Method is superior as NO additional Sodium Chloride is added nor is it concentrated.
The AAP Balling method also eliminates the use of a calcium reactor.
By not using a calcium reactor, this creates some other benefits:
-The pH of the whole tank can be maintained at a higher level, because no acidic calcium reactor effluent are added to the tank anymore.
-The addition of the balling mix provides all the depletion of elements.
Videos explaining the "Balling Method":
Recommended Product Resources (sponsors this hobby with websites such as this):
*AAP Bio-Calcium Original Balling Set; Parts A/B/C.
*SeaChem/AAP Reef Advantage Calcium
Other methods of calcium maintenance include Kalkwasser, Calcium reactors, and products such as "Reef Calcium; polygluconate".
While Kalkwasser is popular among many advanced marine aquarists, caution should be used with this method of adding calcium to your marine aquarium. This is not to say Kalkwasser does not work, in fact introduced properly it is an excellent way to regulate calcium and alkalinity in saltwater aquariums.
Here is how Kalkwasser works:
Used properly Kalkwasser (Calcium Hydroxide) is slowly dripped into your aquarium, it captures free Carbon Dioxide present in the tank water and converts it to Bicarbonate ions.
However if you drip too fast or if there is not enough Carbon Dioxide available in the water, Carbonate ions will be formed which will make the Ca++ you are trying to add to your tank get wasted by the useless precipitation of Calcium Carbonate (often forming a white residue that precipitates out of your aquarium).
This too rapid addition of Kalkwasser may actually cause the Calcium and Alkalinity in your tank to go down instead of up.
See the equation below:
Ca++ + 2(HCO3-) + Ca++ + 2(OH-) <==> 2 CaCO3 + 2 H2O
Often even a slow drip of Kalkwasser (Calcium Hydroxide) can cause the above reaction if there is not enough CO2 present in your marine aquarium.
One method to avoid this is to add 15ml of 5% Distilled White Vinegar (Acetic Acid) into a 1 liter or 1 quart container.
Dissolve 1/2 teaspoon of Kalkwasser into the Acetic Acid, and then dilute to 1 liter (1 quart) volume with either RO/DI water (tank water can be used in a pinch).
A Calcium Generator/Reactor is another popular method for maintenance of calcium and alkalinity as well as KH/pH regulation, especially in marine/reef tanks heavily stocked with stony corals.
A calcium Reactor works by providing a steady stream of calcium (and some Strontium too) by using CO2 in the reactor. The CO2 then "reacts" with the Calcium Carbonate producing calcium ions and carbonate ions (the carbonate ions increase alkalinity).
Although I have NOT had an instance where this was an "essential" device for my reef tanks, it can be very useful for previously noted reasons.
I have also had issues of too much CO2 getting into the marine/reef aquarium resulting in drops in pH and Alkalinity. This is not to say CO2 is "bad" for a marine/reef aquarium as it is needed for photosynthesis in the same way it is needed in a freshwater planted aquarium, however a CO2 level that constantly crashes your pH/Alkalinity is simply too much CO2!
Under normal circumstances/conditions a Fluidized Filter utilizing Oolitic sand media can accomplish similar results, however for high bio load reef tanks with large amounts of stony corals, a Calcium Reactor will produce more calcium.
Kalkwasser and Calcium Reactor Information Referenced from:
*Aquarium Chemistry; Use Of Kalkwasser, Calcium Reactors
Resource for basic but accurate Calcium Test Kit:
API/AAP Calcium Test Kit
Resource high performance Fluidized Sand Bed Filters:
Fluidized Sand Bed Filters from AAP
Which is better Sodium Carbonate vs Bicarbonate?
First what is the chemical difference:
Sodium Carbonate = NaCO3--
Sodium Bicarbonate = NaHCO3- (the "Bi" means two, as in H + CO3)
Next, a little about pH since alkalinity is what generally stabilizes pH in our aquariums. pH = a measurement of H+ and the more H+ the lower the pH and less Alkalinity in short. Molar value wise, it takes twice as much as Bicarbonate as Carbonate to raise the Alkalinity up 1 Equilibrium unit. Volume wise it is 0.6 tsp of Bicarbonate vs. 0.4 tsp of Carbonate to raise the Alkalinity 1 milliequivalent (mEq) / or 2.8 dKH in 10 gals. Weight wise, is it is 3 grams vs. 2 grams.
Bicarbonate, due to that H, has less impact on pH than Carbonate.
Bicarbonate is mostly for raising the Alkalinity along with pH maintenance, while Carbonate is for raising the Alkalinity and pH.
Carbonate used only by itself should only be used if you have a low pH and Alkalinity. If it's to buffer up the Alkalinity, Bicarbonate is better.
Generally in a healthy/balanced reef aquarium where excess CO2 is not being produced or introduced (such as with a Calcium Reactor), a Bicarbonate is the better choice for an ionically blended bicarbonate with other elements in ionic balance such as SeaChem/AAP Reef Builder or used in the balling Method, NOT an economy Soda Ash Sodium Carbonate that is often sold by bulk aquarium supply discounters.
My experience has shown that Soda Ash Sodium Carbonate will not show up as a problem short term, but long term this WILL show up with lower alkalinity reserves and a slowly deteriorating ionic balance over time (unless large water changes are performed regularly with a quality marine salt blend). This will also show up as a less than desirable rH over time.
Recommended Product Resource (sponsors this hobby with websites such as this):
SeaChem/AAP Reef Builder
Sodium (Na+) more or less accumulates over time, as does the SO4 and Chlorides from non-ionically balanced use of calcium supplements, alkaline buffers, and minor/trace elements. This is why water changes are often needed to keep the chemistry in balance even though specific gravity/salinity is "spot on". Hence my recommendation of the AAP Balling Method or ionically SeaChem supplements.
It is common for the pH to drop over night, especially if the alkalinity is less than 8 dKH. This pH drop is from animals and plants giving off CO2 at night. The reason why it may not hold at a lower Alkalinity is also a night thing of animals and plants "leaching" out things more so, which can have a greater impact on the Alkalinity and pH as they yield acids.
A common limnological  term for Alkalinity is ANC ("Acid Neutralizing Capacity"). These affect the pH and Alkalinity. Although it's not often heard of in the aquarium keeping hobby, there's also Acidity, BNC, ("Base Neutralizing Capacity"). It's the opposite of Alkalinity.
Sodium Carbonate vs Bicarbonate; from Manhattan Reefs
This is a term that is not often discussed of late, in part because in my experience mentoring is a dead art, with much of the blame falling on social media and lazy forums
As well while we used to have tests kits for this parameter (such as by Nektonics), there are no longer any direct tests for Alkaline Reserve.
What is Alkaline Reserve? While I will admit to some gray areas in description, I will based part of the description on what my experience and testing has shown over the years.
Alkaline Reserve is the aquarium system's sum-total ability to keep it's pH at a certain point. This goes beyond just alkalinity (KH).
This includes ionic balance, Redox balance, filtration, substrate, and more.
Something I noted by both observations and tests over the years when I had an Alkaline Reserve test kit available is that marine aquariums that had a good alkaline reserve were generally more healthy, had less issues long term. This tanks also have many things in common including good maintenance, use of quality marine salt (such as Tropic Marine, not discount salts), use of good filtration which included a skimmer & true UV Sterilizer, and followed good chemistry maintenance procedures such as outlined in this article.So while there is unfortunately no simple test for this of late, knowing your rH, pH, alkalinity (KH), along with following healthy aquarium maintenance procedures such good filtration, use of protein skimmers and Category A or B UV Sterilizers, you likely will be maintaining this parameter
Many trace and some minor elements are not depleted at the same rate as alkalinity and calcium. In my experience not every reef or even marine fish/FOWLR aquarium is the same when it comes to depletion of trace, minor, or major elements.
There is also disagreement among many with what is a minor, trace or major element with websites such as "Live Aquaria" calling Strontium a major element, where as based on its percentage it clearly falls into the category of minor or trace element.
SEE THE LIST BELOW FOR THE MAKE UP OF THE OCEAN:
- Chloride- 55.03%
- Sodium- 30.59%
- Sulfate- 7.68%
- Magnesium- 3.68%
- Calcium- 1.18%
- Potassium- 1.11%
- Bicarbonate- 0.42%
- Bromide- 0.19%
- Borate- 0.08%
- Strontium- 0.04%
- Fluoride- 0.003%
- Other- less than 0.001%
Regardless of what we call each element, it's important to keep your reef or even fish only marine aquariums as close to natural percentages as possible. Although we often find keeping Calcium slightly higher works to our advantage in the closed system most any marine aquarium is in reality.
For this reason, we need to find a method, which works best for us AND our aquarium, not what seems like the method de-jour of the day. As well, just because something might seem more complex, does not necessarily make it better either. So, if you are a beginner, do NOT feel pressured by the so-called pros in many forums, which insist that it's their way or the highway (this is also not to say their method does not work, only that often these over involved methods do not work any better than more simple methods).
As noted earlier, also be careful of popular economy methods, which use bulk Soda Ash Sodium Carbonate and Calcium, then leave out elements, which often get used in conjunction at similar rates such as Magnesium and Strontium. This is still why I prefer the SeaChem or Complete Balling Method over the Economy dosing, Calcium Reactor, or Kalkwasser methods.
Here are a few key Minor/Trace Elements:
Strontium is provided by SeaChem/AAP Reef Builder and Reef Advantage Calcium in ionic balance, which generally replenishes the Strontium to the correct balance. As well the Balling method naturally replaces the correct balance of Strontium in step 3 if this generally simple method is followed correctly.
Strontium is also replenished with the use of a calcium reactor, but not as often in correct ionic balance. It is NOT replenished with the Kalkwasser method or the economy methods without supplementations and often then ionic balance is NOT achieved from my experience.
Generally if SeaChem/AAP Reef Builder and Reef Advantage Calcium are used OR the complete Balling method, supplementation is NOT necessary.
If your magnesium is regularly depleted or lower than normal (between 1200 and 1400 ppm.), I would question your supplementation methods and quality of marine salt mix used.
As well, the argument I have heard that magnesium should be monitored closely or should be supplemented separately based on the fact magnesium makes up a large percentage of seawater does not " hold water" (pardon the pun), any more that we as humans need to be concerned with nitrogen in the air as it makes up the largest percentage of air molecules (much more than O2).
Again, as I noted earlier, with proper supplementation and reef salt mix use, magnesium is rarely, if ever an issue and even then it is more to keep your magnesium at proper ionic concentration/balances with other salts/elements in the water.
Recommended Resource if needed:
SeaChem/AAP Reef Advantage Magnesium
Iodine often is rapidly oxidized in a marine reef aquarium (not so much a marine fish aquarium).
I have found additional supplementation is necessary even with use of the before mentioned SeaChem/AAP products or with Calcium Reactors, Kalkwasser and most certainly economy bulk methods. However, less supplementation (if any) is needed with the Complete Balling Method.
SeaChem/AAP Reef Iodide
Generally supplementation is not required with normal water changes and/or the use of the Complete Balling Method.
- Molybdenum: Molybdenum is trace element known to aid the biological processes of many of the beneficial strains of bacteria.
- Other/General Trace Elements; There are many more trace elements as per my earlier list (which itself is not a complete list). Generally with products such as SeaChem/AAP Reef Trace, AAP SeaLab, or the Complete 3 Step Balling Method and along with water changes with a quality marine/reef salt mix, these are replenished.
SeaChem/AAP Reef Trace includes the before mentioned Molybdenum too.
Of course starting with a good premium reef salt mix is important as well.
I recommend Tropic Marin Pro Reef Mix from Germany as it is clearly the best, although there are many other good/viable reef capable mixes available as well (& many not so good too).
*SeaChem/AAP Reef Trace
*AAP Bio-Calcium Original Complete Balling Set; Parts A/B/C.
*Premium Tropic Marin Pro Reef Sea Salt from Germany
TO SUM IT UP:
The marine aquarium has to have some basic chemistry understanding to maintain a successful tank. There are a handful of methods, which use different dosing methods, based on science and budget.
The most popular method used is different between different groups/nationalities of reef keepers. While there might be different successful ways to keep aquariums, with many examples, there are methods, which have been proven to be more successful than others, when looking at the details of the tank health.
What I personally find frustrating is not the different methods, often that involve understandable budgets; is rather the insistence by some, often by popular persons in social media that certain aspects are essential while ignoring aspects that would actually make more difference.
Case in point is the myth perpetuated by marketers and then picked by non discerning (or paid off) popular YouTube channels or other social media personalities that the use of DI water is essential for marine reef aquariums, all the while using inferior salt mixes or alkalinity and calcium maintenance methods.
All the addition of a DI chamber does for you is lower TDS somewhat compared to a good RO system and remove ions that would result in a residual higher pH (assuming the pH was high in the tap water).
Saltwater by nature is high in TDS and your tap water has to meet certain standards for toxins such as arsenic, so running a GOOD RO unit (not a cheap poorly made one) should lower your TDS enough to be sure there is nothing toxic of any consequence. Better to then spend your money on better slat mixes and better marine chemistry maintenance rather than doing this part "on the cheap" as many do while wasting their money on elaborate RO/DI systems after falling for the "cut and paste marketing".
Really about the ONLY time you would need this additional DI chamber is if you are on a well with very high nitrates (a good RO system still removes most nitrates) or you are running off from a home water softener unit.
Funny thing is, these same persons who will argue the use of getting every last TDS because they worry about 1 part in a billion of arsenic or similar are the same ones who have argued the use of why they should use a USDA approved silicone for their aquarium instead of a cheap unapproved hardware brand silicone.
Keeping a reef tank as close as possible to natural ocean water conditions has always been the advanced marine keepers goal. With the addition of dosing a third part of trace minerals, which help keep an ionic balance, this really is the closest to natural sea water any aquarium keeper can keep. These minerals listed in this Reef Chemistry Article and the suggestions on how to maintain, really are the best current professional advice anyone can take and apply to their reef tank.
Other Recommended Reference & Product Sites
PUR or RQE, YouTube Video Fail- Guide to lighting a planted tank
Saltwater Aquarium Information; Basic to Advanced
Aquarium or Pond UV Sterilization
AquaRay Ultra Premium Aquarium LED Lights
Highest in PUR, The ONLY LED with an IP67 rating or higher for water proofing along with a full 5 year warranty to back them up! Why purchase brands without this rating such as the Finnex, Current, or Fluval only to be essentially placing an electronic light emitting device over your humid aquarium with little or no guarantee? In the long term, you WILL PAT MORE!
TMC Premium Fluidized Sand Bed Bio Filters
Premium, second to NONE Aquarium Bio Filters, that with Oolitic Sand also maintain essential marine aquarium calcium levels, alkalinity, & electrolytes that are important to ALL Marine life, Goldfish, African Cichlids, Livebearers & more
San Francisco Bay Brand Seaweed Salad
"Seaweed Salad" is much more nutritious than spinach and lettuce. This product is recommended for all saltwater Damsels, Clownfish, and especially Marine Angels and Tangs
TMC V2 RO Filter systems; the very best you can buy with TDS meter (far superior to 4 stage RO/DI systems sold via Bulk Reef Supply, Amazon, or eBay that use the inferior cellulose triacetate membrane made by Dow):
Reverse Osmosis Aquarium Water Filters; with TDS Meter
Hydor Smart Wave Controller
• Promotes a healthy reef aquarium or similar aquarium environment where wave action is desired by recreating natural currents found in nature
• Synchronous program for currents typical of barrier reefs and alternate for tides
TMC Advanced Venturi Saltwater Protein Skimmers
A High performance, quality protein skimmer incorporating a patented venturi injection system which optimizes the perfect mixture of fine air bubbles and water and ensures intensive, efficient skimming and the removal of proteins and other harmful toxins (waste) from the aquarium.