The “How To” Guide to Reef Aquarium Chemistry for Beginners,
Part 1: The Salt Water Itself


This article is the first in a series that deals with coral reef aquarium chemistry issues on a basic and practical level.  Its primary purpose is to get new aquarists to focus on those aspects of reef aquarium chemistry that are truly important, instead of on those that are not.  New aquarists are bombarded with a huge assortment of issues and opinions relating to aquarium husbandry practices, and none seems to cause more anxiety than chemistry issues.  Some of these issues are actually very complicated, and the answers to many questions are simply not known.  Fortunately for hobbyists, knowing the answers to these questions is rarely important to keeping a wonderful reef aquarium.  Those issues that are important to understand are much more straightforward and can be solved without excessive anxiety.

The first lesson that extends to nearly every aspect of reef aquarium husbandry is not to panic.  The second is to realize that there is almost never a single “perfect” way to do something.  Luckily, there are often many suitable ways to deal with reef chemistry issues.  Like the many available roads for driving from New York to San Francisco, many paths will get you there.  Some are more pleasant, some are more expensive, some have inherent risks, some are genuinely poor choices, and some are dead ends, but many, many paths will work out just fine.  Nearly all have been trodden by the army of reef aquarists ahead of you, so, fortunately, you have a large amount of experience to draw upon. 

These articles are not intended to be a roundup of appropriate reef aquarium chemistry parameters, which have been covered in previous articles.  They also are not intended to be a discussion of what seawater is composed of, as that, too, has been previously discussed.  In many cases, however, these issues will be touched upon to set the framework for understanding why certain husbandry actions are appropriate.

This first article focuses on some of the first chemistry issues to face beginning coral reef aquarists:

  • What brand of salt should I use?
  • How do I make artificial seawater?  
  • What is salinity? How do I measure it? 
  • Do I need to purify the tap water?
  • What about natural seawater?

The full set of articles in this series is expected to include:

The “How To” Guide to Reef Aquarium Chemistry for Beginners

  • Part 1: The Salt Water Itself
  • Part 2:  What Chemicals Must be Supplemented
  • Part 3:  pH
  • Part 4:  What Chemicals Must be Monitored to Prevent Buildup

The sections of this article are:

Introduction to Seawater Salinity


Seawater is approximately 96.5% water and 3.5% salt, by weight.  When the salinity of seawater is referred to as being 35 ppt (parts per thousand), that is the same as saying 3.5% salt.  Seawater is composed of many different ions (salts), with the total of all adding up to the 3.5%.  Some ions are present at very high concentration and some at very low concentration.  However, even those present at very low concentration can be important to organisms living in the water.

When salts are dissolved in water, a variety of the water's attributes change, including its density, its refractive index and its conductivity.  All of these changes can be used by aquarists as a way to measure the total amount of salt in solution.  Consequently, aquarists need not dry out water to find the salinity by the amount of salts that remain behind, but can simply rely on tools that measure these other attributes (see below).

The main ions in seawater, in order of percent by weight, are chloride, sodium, sulfate and magnesium.  These are the salts that determine salinity by how much of them is present.  Changes in the concentrations of all of the other ions put together have little impact on salinity, although they may otherwise be very important.

Natural Seawater for Coral Reef Aquaria


Natural seawater can be a fine source of water for a coral reef aquarium.  Many aquarists collect it themselves if they live near an ocean.  The most important factors are how pure it is when collected, and how pure it remains until used.  It is often suggested to collect the water offshore to avoid run-off and other pollution sources although even offshore waters can have unwanted organisms and chemicals in them.  The next best is to collect it from a rising tide from a jetty or other means, to get a bit away from shore.  There can be risks to using coastal waters. Depending on the location there could be enough chemicals or pathogens to harm the tank.  Also, even far from shore there may be elevated nutrients and salinity that deviates significantly from “pure” seawater.

One issue with natural seawater is that it contains suspended organic molecules, bacteria, phytoplankton and other organisms.   In most cases, these will not hurt an aquarium and may actually provide food for many reef aquarium inhabitants.  But if the water is stored and allowed to stagnate, the breakdown of these organic materials can produce toxic compounds such as ammonia and hydrogen sulfide.  For this reason, storing natural seawater is usually preceded by filtration, and even sterilization processes in some cases.  It is beyond the scope of this article to detail these procedures, but aquarists storing natural seawater should be aware of these concerns and seek out additional resources to deal with these issues. For those interested in further details, Martin Moe mentions how to treat and store seawater in his Beginner to Breeder book and also his Marine Systems book.   

One word of caution is in order.  Some companies collect and sell natural seawater.  However, it appears that in some cases this water is not handled as well as it might be.  One company, for example, has had significantly elevated lead and zinc in its water, suggesting possible exposure to metals in the collection or handling process (see analyses studies linked below).  Consequently, not all “natural seawater” is the same. 

Artificial Seawater


Most marine aquarists use artificial seawater for their aquaria.  This is usually made by combining a commercial mixture of appropriate salts with suitably pure freshwater.  A very few aquarists may make their own salt mixes, but unless you have access to commercial chemicals, and unless you make very large amounts, this work is neither cost effective, nor does it have clear benefits.

“Sea salt” that is often sold to consumers for various purposes (such as cooking) cannot be used.  Regardless of the fact that it sounds to many people like it should work, it does not match real seawater, and often is not even close.  Often, its magnesium levels are tenfold lower than natural seawater, for example, so don’t go that route.

Artificial Seawater: Which Mix?


One of the first things that most marine aquarists ask is, “Which mix?”  Many are commercially available; some are widely used, and some less so.  Many aquarists just use the cheapest one that their local stores have in stock.  But what evidence is there about which salts are best?

To be honest, the evidence for using one salt mix over another is marginal at best.  Certainly some are better, and some may be downright undesirable, but no simple ranking can be made.  Every artificial salt mix varies from natural seawater's concentrations of some ions.  Amazingly, many that claim to try to match seawater actually do a surprisingly poor job, and differ significantly.  Sometimes this deviation from nature is intentional, although most aquarists don’t even know how their mixes deviate. I sometimes think the companies don’t always know either, based on their public and private comments about their own salt mixes. 

A variety of factors prevent companies from exactly matching seawater's concentrations of many of the minor and trace elements in seawater.  The biggest of these is cost.  The four big ions in seawater (sodium, chloride, sulfate and magnesium) must be added in large concentration to seawater.  Unless they are very pure (and very expensive), these primary ingredients will contain impurities that rise to the level of, or even exceed, the levels of other ions naturally occurring in seawater.  So companies work as best they can, within reasonable cost constraints, to control impurities to appropriate levels.  More expensive salt mixes can theoretically do a better job by purchasing purer raw materials, but that does not ensure that those companies do so.

Artificial Seawater: Chemical Analysis of Mixes


Several studies have analyzed the chemical constituents of salt mixes.  Some of these are linked below for those who want to investigate further.  

The problem with using such studies to select a salt mix is that, while we can look to see which brands most closely match natural seawater, the problem is that none really does, and it becomes very difficult to decide what is best.  For example, is it better to have too much sulfate or too little fluoride?  Too much borate or too little bromide?  Too much strontium or too little potassium?  No one knows.  Ask that question about nearly every chemical constituent, and the true answer is, “No one knows.”

Even worse, salt mixes periodically change their formulations and bulk material suppliers so their properties change.   Even if a salt study analyzes so many samples that it accurately reflects all of the batches of a single salt brand on the market at a given time, a few months later it may be of little value.  Several manufacturers, for example, have publicly stated that they have changed their formulation since some of the studies linked above were released.

There are some obvious chemical differences between salt mixes that aquarists readily discover for themselves.  These generally relate to their readily measurable levels of calcium, alkalinity and magnesium.  Even here, it is not simple to decide what is best because aquarists often intentionally keep water parameters that are different from natural seawater (for example, maintaining higher alkalinity than in the ocean), or might want the mix to have an overabundance of something to offset losses in the aquarium (magnesium, for example).  Bear in mind that all of these, and most especially alkalinity, are almost immediately altered in reef aquaria by the necessary supplementation, and that the exact values in the salt mix may not be particularly important.  They are also easily adjusted by aquarists who want to do so.

So, despite being a chemist and having taken many of these types of measurements myself, I don’t put much emphasis on such chemical studies.  Perhaps it would be wise to toss out of contention those that seem seriously flawed, but that leaves many of them.  Better salt mix decisions might be made using the types of information described later in this article. 

Artificial Seawater: Biological Analysis of Mixes


At least a couple of studies have also examined salt mixes from a biological perspective.  That is, they looked at the effects of different salt mixes on organisms living in them.  These are linked below for those who want to pursue them, although the final results from Eric Borneman’s study (second two links) have not yet been published.   

In theory, these sorts of studies have an advantage over full chemical analyses in that, for at least the specific biological endpoints being examined, they rank order different types of seawater from best to worst.  For example, those causing the least fish diseases, faster coral growth, least chance of growing pest algae, etc.  Such information could be very valuable.

However, running high quality studies is immensely costly and time consuming.  In short, it is similar to running many identical reef aquaria in parallel, and comparing them in one or more important ways.  In practice, the compromises made sometimes weaken the usefulness of the conclusions.  The concern, in my opinion, with these types of studies is two-fold:

1.  The organisms tested sometimes do not represent those that aquarists typically grow.  For example, sea urchin embryos have been used for this type of study by Ron Shimek (first study above).  However, few reef aquarists rear sea urchin embryos.  If a salt mix is not optimal for sea urchin embryos, but results in high quality reef aquaria (like those represented by Reef Central Tanks of the Month), is that an important factor in selecting a salt mix?

2.  Both of the studies linked above use salt mixes in ways that are not used by reef aquarists; for example, using 100% raw artificial saltwater (Shimek’s study above), or using monthly water changes with 100% raw artificial seawater as the only method of nutrient export and calcium import (Borneman’s study above).  I’ll pick one chemical issue to play the straw man with this type of study, but other similar concerns are equally valid. 

From the types of chemical analyses described in the previous section, for example, we know that many salt mixes contain potentially stressful levels of ammonia, present as an impurity (say, 0.17 ppm in Instant Ocean).  In a normal reef aquarium, this ammonia is diluted out, and easily and rapidly removed by nitrifying bacteria.  For example, using it for a 10% water change will boost ammonia only to a safer 0.017 ppm.  But these studies used it for 100% water changes, and one of the cases (Shimek's study above) provided no nitrifying capacity at all.  Consequently, the results of these studies may not reflect aspects of the salt mixes that are important in normal use, but may be important only in specialized lab tests.

In a recent commentary on his study, Borneman stated:

“I will say that, at least from being familiar with the data and the appearance of the tanks and the survival and appearance of the species that there are certainly some salts I would prefer to use in my tank and some that I probably wouldn't use again, even though I have used them for many years without any obvious negative effects. I have a feeling that the reason these differences are not observed by those using these salts, myself included, is that the complexity of the reef tank community is able to mitigate the good and bad aspects of the salts that became apparent in a more controlled environment.”

I certainly agree with at least the second half, and think it supports the message that I am trying to get across to beginning aquarists: home reef aquarium “quality” should be the arbiter of what is a suitable salt mix, not a lab test that purports to show effects that may not be reproduced in real home aquaria.

Artificial Seawater: Real Aquariums and Salt Mixes


So, if we cannot rely exclusively on chemical and biological testing of salt mixes as a guide to selection, what can we use?  Well, we can obviously look to see what other reef aquarists are using.  But, of course, you’d want to select mixes that have resulted in success.  Unfortunately, a “poll” of aquarists may simply reflect what they use, not what they are successful with. It may also include a lot of votes from aquarists who have not yet had the aquarium long enough to deem it a success or those who have not used more than one or two brands.

Here’s a related suggestion.  I looked through the past five years of Reef Central's Tanks of the Month, and recorded what salt mixes they used.  Here's what I found (Table 1):

Table 1.  Salt mixes used in the past five years of Reef Central's Tanks of the Month.

Salt Mix

Number of Examples

Unidentified

>30

Instant Ocean

9

Reef Crystals

7

Tropic Marin

5

Tropic Marin Pro

2

Oceanic

2

Red Sea

2

Coralife

1

Catalina Water Company

1

Seachem

1

Sera

1

Preis

1

I propose that the exact numbers and ranking are not too important, as they reflect aquarists' choices, costs, and perhaps general availability, as opposed to the “betterness” of salt mixes.  However, any mix used in any Tank of the Month shows that it can facilitate a wonderful aquarium.  Further, picking one of the more commonly encountered mixes in Table 1 may be prudent, because more than one aquarist has shown that a beautiful and successful aquarium can be attained using one of them.  So, my suggestion is to pick one of the top half dozen mixes above, and then don’t spend any more time worrying about whether your mix is the “best” one or not.  I have used Instant Ocean for more than 10 years, largely because it has had a long and wide track record of success.

What Water to Use to Make Artificial Saltwater?


In addition to using a suitable salt mix, it is important to use suitably pure freshwater, both for making salt mixes and for topping-off for evaporative losses.  The majority of experienced and successful reef aquarists in the U.S. appear to use RO/DI (reverse osmosis/deionization) to purify tap water.  I also use it.  A properly functioning RO/DI filter is always adequate to purify tap water that is otherwise drinkable. Many brands of these filters are available.  Choosing one is not trivial, as they can have significant differences and the better units normally cost significantly more than stripped down models.  It is beyond the scope of this article to detail all of the important attributes of good RO/DI systems, but they have been covered in previous articles.  It is neither necessary nor desirable to add anything to RO/DI water or to any type of freshwater used to make a salt mix (or aquarium top-off to replace evaporation), unless you determine that after adding the salt, the water is deficient in something.

Reverse osmosis (RO) alone may be adequate in some cases, but is clearly not appropriate in others.  In particular, if the local water company uses chloramine to disinfect the water, then the effluent from an RO-only system will contain substantial ammonia.  If the tap water has copper at the high end of the normally encountered tap water range (> 1 ppm), RO alone may also be inadequate.

The use of tap water itself entails a number of concerns besides the presence of chlorine.  First is chloramine, which does not dissipate after sitting around, the way many aquarists have done in the past for chlorine.  It is now being added to many water supplies, and is much longer lived than chlorine.  It also requires special treatments, not just the standard dechlorinating agents.  Other concerns with tap water are copper (which often comes from your home's plumbing), nutrients (nitrate and phosphate) and alkalinity (which is not per se a problem, but can boost levels too high in some cases).  In general, I recommend avoiding tap water.  Sure, some folks use it and have fine aquaria.  That does not, however, prove that any other tap water, even from a neighboring home, is suitable.

The best distilled water is perfect for our applications. Typical commercial distilled water is likely acceptable, as long as it has not been exposed to metals such as copper in condensers, pipes or holding tanks.  Unfortunately, it is not easy to know the production history of distilled water, and testing with most copper test kits may be inadequate because they may not accurately read low enough to detect its presence.

Many aquarists use water provided by machines at grocery stores or from their local fish stores.  Many of these are apparently reverse osmosis (RO) water.  That is, again, likely okay, with the same caveats as for distilled water and RO water and in these cases it is unlikely that the aquarist can determine the proper maintenance of the filtration systems.  Sometimes a chemical analysis can be provided by the supplier of such water, but frequently that is not available.

What Salinity to Use?


For reference, natural ocean water has an average salinity of about 35 ppt, corresponding to a specific gravity of about 1.0264 and a conductivity of 53 mS/cm.  Salinity, however, does vary substantially from place to place.

As far as I know, little real evidence suggests that keeping a coral reef aquarium at anything other than natural salinity levels is preferable. It appears to be common practice to keep marine fish, and in many cases reef aquaria, at somewhat lower than natural salinity levels. This practice stems, at least in part, from the belief that fish are less stressed at reduced salinity. Substantial misunderstandings also arise among aquarists as to how specific gravity really relates to salinity, especially considering temperature effects.

The salinity on natural reefs has been discussed in previous articles. My recommendation is to maintain salinity at a natural level. If the organisms in the aquarium are from brackish environments with lower salinity, or from the Red Sea with higher salinity, selecting something other than 35 ppt may make good sense. Otherwise, I suggest targeting a salinity of 35 ppt (specific gravity = 1.0264; conductivity = 53 mS/cm).

Fortunately, coral reef aquaria seem rather forgiving with respect to salinity.  The range of salinities encountered in what most would proclaim as successful reef aquaria is actually quite large.  Don’t agonize over small deviations from natural seawater.  You will not notice any benefit changing from 36 or 34 ppt to 35 ppt (specific gravity = 1.0256 to 1.0271).  Many fine reef aquaria appear to run at salinity levels as low as 31 ppt (specific gravity = 1.023), but bear in mind that the values that aquarists report (as well as your own measurements) are fairly likely to be inaccurate, so pushing the low or high end of the range may not be prudent. 

Bear in mind that if aquarists target salinity values different than 35 ppt, the amounts of calcium, magnesium, alkalinity, etc., will all likely deviate from natural levels as well.  For example, making artificial seawater to a low salinity will normally result in low values for these parameters and may require adjustments.

How to Measure Salinity


There are a variety of different ways to measure and report salinity, including refractometers (Figure 1), hydrometers (Figures 2-4) and conductivity probes (Figure 5). These devices typically report values for specific gravity (which is unitless) or salinity (in units of ppt or parts per thousand, roughly corresponding to the number of grams of dry salt in 1 kg of the water), although conductivity (in units of mS/cm, milliSiemens per centimeter) is sometimes used.

Figure 1. A schematic drawing of a typical hand held refractometer used to measure salinity.

Figure2Beginners1.jpg Figure3Beginners1.jpg Figure4Beginners1.jpg
Figures 2 - 4. The measurement section of a Tropic Marin floating glass hydrometer (left). The Tropic Marin floating glass hydrometer, showing that it is expected to be used at 77°F (center). A SeaTest swing arm hydrometer (right).
Beginners1Figure5.JPG
Figure 5. A Pinpoint selectronic salinity (conductivity) meter.

All of these devices can be suitably accurate, and all can be inaccurate, especially if not used or calibrated appropriately (and sometimes even when calibrated properly, depending on the quality of the device).  Whichever device is chosen, I recommend that it be checked at least once in a solution that is close to seawater's salinity.  These can by DIY or commercial fluids (which can also vary in quality and accuracy).  Checking these devices in pure freshwater can be inadequate, even if manufacturers (especially refractometer manufacturers) recommend that it is suitable; often it is not.

Among the least expensive of these are swing arm hydrometers.  Unfortunately, they are often inaccurate and are rarely calibrated or checked by aquarists.  Quality glass hydrometers, refractometers and conductivity meters (electronic salinity meters) are all somewhat more likely to be accurate, if only, in part, because they are more frequently calibrated or checked for accuracy by aquarists. 

Temperature has little effect on seawater's salinity or specific gravity, but can impact and cause errors in the measurements themselves.  Effects on the measurements are not generally a big problem, except for floating glass hydrometers and refractometers that do not automatically compensate for temperature (many do).  Hydrometers, especially, are often made for other industries and are designed with the expectation of being used at 60° F or other temperatures far from normal reef tank temperatures, potentially causing significant errors.  Refractometers depend on small volumes (drops) of water, and so if the refractometer has any seawater left on its prism, the next time it is used, the small amount of salt will dissolve in the newly added drops of water causing false readings. Thus, refractometers should be rinsed in distilled water and dried carefully.  Rapid reading of the refractometer may also be useful to reduce the chance for evaporation to increase the salinity.

TDS meters are conductivity meters, but often they do not have the range to read marine aquarium salinity.  In other words, they are designed to read the conductivity in freshwater, and cannot typically extend their readings up to the tens of thousands of ppm of total dissolved solids (TDS) needed to monitor seawater salinity. 

How to Mix Artificial Seawater


First, add the freshwater to the mixing container.  The container can be any size, but larger containers will be less likely to have “off” parameters caused by taking a small portion of a container of salt mix that may not be representative of the bucket or bag due to settling.  I make up 88 gallons at a time.  Assuming that it is made from adequately pure freshwater, mixed artificial seawater can be stored for as long as needed without continuous stirring or heating.  I keep mine for a few weeks completely unstirred after initial mixing.  It will not become anaerobic (although used tank water or natural seawater may become anaerobic due to the breakdown of organics in it, and should not be stored unaerated).

Do not add anything other than salt mix to the freshwater unless you determine, after mixing in the salt, that it is deficient in something important.  Add the salt and stir. Adding the salt before the water can be okay, but causes an unusually high salinity for the period when you are adding water, which can result in the formation of certain precipitates that may be hard to redissolve.

Overnight stirring with a powerhead is a good way to dissolve the salt, but shorter stirring can be okay, if done vigorously.  If you are using the saltwater for very small water changes (2% or less at once), you need not heat it.  If you want to add any calcium (I do), magnesium (I do), alkalinity (I don’t) or anything else (not recommended), add it after the salt has dissolved.  The overnight stirring will also help with aeration, which can be useful for some mixes that start with a high pH and need to pull in CO2 from the air to reach normal pH.  After aeration, the pH is determined only by the alkalinity and the ambient carbon dioxide level in the air.  It is not an attribute of the salt mix.  More details on pH will be covered in a future article.  Aeration also pulls in oxygen, if the starting freshwater was deficient in oxygen.

Measure the salinity, and then adjust it by adding more salt mix or more water as necessary to reach your desired salinity.

Summary of Suggestions for the Saltwater


The following guidelines provide a short synopsis of the important conclusions from this article:

1.  Don’t focus on perfect salt mixes (none exist), or any other chemical attribute of coral reef aquaria.  Focus on attainable suitability.

2.  Natural seawater might be a fine choice for a coral reef aquarium.  If using natural seawater, be sure it is collected, treated and stored in a suitable manner.

3.  Artificial seawater is another fine option.  Don’t get worked up by every salt mix comparison that comes along.  If you find one that seems important, make sure that it reflects things with real world importance, and that it uses salts in a way that aquarists typically would.  A variety of brands of salt mix have been used successfully by a large number of aquarists, including Reef Crystals, Instant Ocean and Tropic Marin (Pro and regular).  If you select one of these, it is unlikely that any failures you will encounter will relate to a problem with the salt mix.

4.  Use appropriately pure freshwater to make the salt mix and top-off for evaporation.

5.  Use an appropriate device, appropriately calibrated, to measure salinity.  I recommend targeting natural ocean salinity (S=35 PSU or 35 ppt, specific gravity = 1.0264).  But salinity is fairly forgiving, and a range around these values is certainly acceptable.

Conclusion


Attaining initially suitable seawater for a coral reef aquarium is an important aspect of coral reef aquarium husbandry.  It need not, however, require an overly complicated exploration of chemical and biological testing.  Following in the footsteps of highly successful reef aquarists is a fine way to proceed.  Using that type of information, this article provides the basics necessary to obtain suitable aquarium water to start with.

Of course, that water quickly becomes depleted in some chemicals, and polluted with others.  Subsequent articles in this series will provide details on how to deal with those issues in ways that are tried and true, and not overly complicated.

In the meantime,

Happy reefing!



If you have any questions about this article, please visit my author forum on Reef Central.




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The “How To” Guide to Reef Aquarium Chemistry for Beginners Part 1: The Salt Water Itself by Randy Holmes-Farley - Reefkeeping.com