Inland Reef Aquaria Salt Study Part II

Summary From Last Month

There are three separate areas to
be addressed:

  1. Does the manufacturer’s data hold up to close
    scrutiny?
  2. Are there heavy metal concentrations revealed in these
    tests that could account for Dr. Shimek’s bio-assay
    results?
  3. Do these results shed any light on the salt mix choices
    available to the hobbyist?

Validity of Manufacturer Supplied Data

Here are the values we measured for Crystal Sea Bio-Assay
compared to the manufacturer’s data used in Dr. Shimek’s
study. Only those elements where data is available from both
sources are included in the table. All values are in ppm.

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ElementManufacturer DataMeasured LevelsDifference
Aluminum0.170.032– 81%
Barium0.050.029– 42%
Calcium410320– 22%
Chromium0.0010.009+ 800%
Cobalt00.00058
Copper0.0010.006+ 500%
Lead0.0040.0009– 78%
Lithium0.1112+ 10,809%
Magnesium12901600+ 24%
Manganese0.0010.024+ 2,300%
Molybdenum0.010.006– 40%
Nickel00.0158
Potassium380300– 21%
Sodium1040010500+ 1%
Strontium12.56.4– 49%
Titanium00.0088
Vanadium0.0020.058+ 2,800%
Zinc0.0140.021+ 50%

The same table is repeated here for Bio-Sea MarineMix. There
are fewer values since there were several elements listed as
“no data” in the Shimek study.

ElementManufacturer DataMeasured LevelsDifference
Aluminum0.200.032– 74%
Calcium430320– 23%
Chromium0.030.009– 67%
Cobalt0.030.0005– 93%
Copper0.040.006– 83%
Lead0.040.0009– 98%
Lithium3.1312– 96%
Magnesium13361600– 10%
Manganese0.0120.024+ 33%
Molybdenum0.0730.006– 99%
Nickel0.020.015– 60%
Potassium379300– 34%
Sodium1025210500– 8%
Strontium9.756.4+ 23%
Zinc0.0120.021+ 108%

Note that for many of the elements, these salt mixes actually
measured lower than the manufacturer’s data. In order to get
the significantly higher values for Instant Ocean reported in Dr.
Shimek’s study, the data from the Atkinson and Bingman study
for Instant Ocean must have shown significantly higher metals
levels than we found. We have been able to confirm that there
have been several formula changes to Instant Ocean since 1999.
Accordingly, here is a comparison of the 1999 study values for
Instant Ocean and our results.

Element1999 Study LevelsMeasured LevelsDifference
Aluminum6.480.033-19,536%
Barium0.0120.014+ 14%
Calcium361340– 6%
Chromium0.390.004– 9,650%
Cobalt0.0770.0005-15,300%
Copper0.1140.005– 2,180%
Lead0.4350.0008– 54,275%
Lithium0.3750.25– 50%
Magnesium12641400+ 10%
Manganese0.0660.019– 247%
Molybdenum0.1730.001– 17,200%
Nickel0.10.003– 3,233%
Potassium367300– 22%
Sodium106219400– 13%
Strontium16.6510– 67%
Titanium0.0320.009– 256%
Vanadium0.1480.066– 124%
Zinc0.0330.025– 32%

There is sufficient variation between the measured values and
the manufacturer’s data to call into question the accuracy of
that data for both Crystal Sea Bio-Assay and Bio-Sea MarineMix.
However, it is clear that the vast majority of the error
between this study and Dr. Shimek’s study is not due to the
manufacturer’s data on these two salts, but the use of data
from an old study that no longer represents the true composition
of Instant Ocean
.

Metals Levels & Bio Assay Results

In order to explain the bio-assay results in terms of metals
toxicity there would have to be metals in Instant Ocean that are
at a substantially higher concentration than that found in
Crystal Sea Bio-Assay or Bio-Sea MarineMix. Here is a summary of
Instant Ocean’s metals level compared to the other two salts.
Elements below the detection limit for all salts are excluded
from the table.

ElementInstant OceanCrystal Sea Bio-AssayBio-Sea MarineMix
LevelComparisonLevelComparison
Aluminum33 ppb32 ppb3% lower52 ppb58% higher
Antimony0.5 ppb2 ppb300% higher0.5 ppbsame
Arsenic54 ppb65 ppb20% higher67 ppb24% higher
Barium14 ppb29 ppb107% higher20 ppb43% higher
Cobalt0.5 ppb0.5 ppbsame2 ppb300% higher
Chromium4 ppb9 ppb125% higher10 ppb150% higher
Copper5 ppb7 ppb40% higher6 ppb20% higher
Lithium0.25 ppm0.12 ppm52% lower12 ppm4,700% higher
Manganese19 ppb24 ppb26% higher16 ppb16% lower
Molybdenum1 ppb1 ppbsame6 ppb500% higher
Nickel3 ppb15 ppb400% higher8 ppb167% higher
Lead0.8 ppb0.9 ppb13% higher0.8 ppbsame
Palladium4 ppb0.5 ppb88% lower5 ppb25% higher
Rubidium55 ppb49 ppb11% lower59 ppb7% higher
Selenium140 ppb61 ppb56% lower190 ppb36% higher
Strontium10 ppm6.4 ppm36% lower12 ppm20% higher
Titanium9 ppb8 ppb11% lower2 ppb78% lower
Vanadium66 ppb58 ppb12% lower87 ppb32% higher
Zinc4 ppb4 ppbsame0 ppb*N/A

* The Zinc level of Bio-Sea MarineMix measured 21 ppb, but was
zero after subtracting the 21 ppb Zinc measured in the RO/DI
water.

As can be seen in the numbers, Instant Ocean does
not
have consistently higher metals levels than Bio-Sea
MarineMix or Crystal Sea Bio-Assay. In fact, it has significantly
lower metals levels than Bio-Sea MarineMix. Compared to Crystal
Sea Bio-Assay, Instant Ocean is lower in eight elements and
higher in eight elements, but the difference is generally greater
on those elements where Instant Ocean is lower.

In fact, that there is only a single element where Instant
Ocean tested higher that both of the other salts: Titanium.
However it should be noted that the levels in Instant Ocean were
on par with Crystal Sea Bio-Assay (9 ppb vs. 8 ppb).

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If differences of less than 20% are excluded, the comparison
is as follows:

Instant Ocean vs. Crystal Sea
Bio-Assay
Instant Ocean vs. Bio-Sea MarineMix
IO less than CSBIO greater than CSBIO less than BSMIO greater than BSM
AntimonyLithiumAluminumTitanium
ArsenicPalladiumArsenicZinc
BariumSeleniumBarium
ChromiumStrontiumCobalt
CopperChromium
ManganeseCopper
NickelLithium
Molybdenum
Nickel
Palladium
Selenium
Vanadium

With these numbers it is difficult to attribute Dr.
Shimek’s results to metals toxicity. There is a great need to
determine if Dr. Shimek’s results can be repeated, not only
with the four original salts, but others as well. Assuming the
bio assay results are repeatable then a root cause remains
elusive. From this data, it appears conclusive that toxic metals
contamination is not the culprit.

What is the Best Salt?

A worthy goal for any artificial salt mix would be to create a
sea water solution which is as close as possible to natural sea
water. Unfortunately, no salt in this study comes very
close to meeting this goal
. Assigning
“weights” to each element in order to mathematically
determine a best salt is fraught with immense difficulty. Who can
say with quantitative certainty which elements are more important
to the life in our tanks? Are excess Copper levels worse than
excess Arsenic levels? Is a Strontium deficiency more or less
critical than a Magnesium deficiency? There are hundreds of such
questions that could be argued endlessly. We will not attempt it.
We can, however, note those pieces of data that “stick
out” and try to summarize which salts seem to get which
elements right, i.e.; are closest to NSW levels or correctly
minimize the subjectively “bad” elements and elevate
the subjectively “good” ones.

Specific issues of concern are:

  • Instant Ocean, Crystal Sea MarineMix and Crystal Sea
    Bio-Assay all mix to an unnaturally high pH. A major water
    change followed by the addition of kalkwasser or the rapid
    addition of a buffer additive could create an undesirable pH
    peak.
  • Oceanic Sea Salt has abnormally high levels of Aluminum,
    Manganese, Nickel and Zinc. It also has a Strontium deficiency,
    but is otherwise similar to the other salts. Some type of metal
    contamination seems a possibility.
  • Bio-Sea MarineMix has unusually high levels of Aluminum and
    Vanadium.
  • Crystal Sea MarineMix has high levels of Antimony, Boron,
    Lithium, Lead, Palladium, and Titanium. Like Oceanic, it is
    also deficient in Strontium.
  • AquaMedic Sea Salt has Barium levels roughly double the
    other salts, as well as notably high Bismuth, Cobalt, Lead,
    Selenium and Titanium.
  • Omega Sea Marine Salt has the highest levels of Copper,
    Chromium, and Arsenic of all the salts tested. Its Vanadium
    levels are similar to Bio-Sea MarineMix.
  • Tropic Marin Sea Salt has high Copper and ties with Omega
    Sea for the highest Chromium levels.
  • Instant Ocean has the highest Titanium level. Its Aluminum
    level is also high, but less than half of the highest salt mix
    (Oceanic).
  • Kent Marine Sea Salt shares the Aluminum levels of Instant
    Ocean and Crystal Sea Bio-Assay, it is high, but less than half
    of the worst level for that element. Its Antimony and Chromium
    levels are also high.
  • Crystal Sea Bio-Assay has the highest Lithium and Nickel
    levels of any salt tested. It shares the moderately high
    Aluminum levels of Instant Ocean and Kent Marine, and also
    matches Kent Marine in high Antimony and Chromium.

The table below is our attempt to note those salt mixes with
element levels that come close to natural sea water, are low when
the element is undesirable, or are high when the element is
desirable. This is the about as close as we can come to
“picking a winner” but it does involve some judgment
calls on our part. Please do not select a brand of sea
salt based solely on this table!

ElementAMOOSBSMCSMTMIOKMCSB
Aluminum****
Antimony******
Arsenic***
**
Boron***
Barium********
Bismuth********
Bromine*****
Calcium*********
Cobalt*****
Chromium***
Copper****
Iodine*********
Potassium*********
Lithium*******
Magnesium*******
Manganese********
Molybdenum******
Sodium*********
Nickel****
Lead**
Palladium**
Rubidium*********
Sulfur
Selenium***
Silicon********
Strontium*******
Titanium*****
Vanadium
Zinc*****
Total Score151517141722212217

Conclusions

  • Bio-Sea MarineMix and Crystal Sea Bio-Assay do not have
    significantly lower heavy metals than Instant Ocean. In many
    cases, Instant Ocean is actually lower in toxic metals. The
    root cause of Dr. Ronald Shimek’s bio-assay results remains
    unknown.
  • The manufacturer’s data for Bio-Sea MarineMix and
    Crystal Sea Bio-Assay used in Dr. Shimek’s study does not
    accurately represent the elemental composition of these salts.
    However, a far larger discrepancy was found with the 1999
    Atkinson and Bingman data for Instant Ocean. It is believed
    that this difference is due to formula changes in Instant Ocean
    since the 1999 study.
  • No salt in this study is an accurate simulation of natural
    sea water. All salts had at least one toxic heavy metal that
    was far in excess of NSW levels. When all factors are
    considered, Tropic Marin, Instant Ocean, and Kent Marine score
    the best, but such a score can not be arrived at without some
    amount of subjective judgment in evaluating the pertinent
    factors.

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References

  1. Atkinson, M. and C. Bingman 1999. The Composition of
    Several Synthetic Seawater

    Mixes. Aquarium FrontiersOnline. March,
    1999
  2. Inland Reef and Ron Shimek 2001. Analysis of TLF Combisan.
    Reefs.org online article library
    (http://www.reefs.org/library/article/combisan_analysis.html).
  3. Shimek, R. L. 2003. The Toxicity of Some Freshly Mixed
    Artificial Sea Water; A Bad Beginning For A Reef Aquarium.
    Reefkeeping.com. Volume 2. Number 3. March, 2003.
  4. Randy Holmes Farley 1998. Understanding Seawater. Aquarium
    Frontiers Online. July, 1998

Appendix

For certain elements, there was little difference found
between any of the salt mixes. The data for these elements are
presented herein.

Arsenic (ppb)

Arsenic levels were not reported in Dr. Shimek’s study.
All salt mixes measured more than ten times higher than NSW, but
there was no significant difference between salt mixes.

Arsenic

Calcium (ppm)

Calcium is essential for the growth of most marine organisms,
especially stony corals. It is a metal and therefore a potential
contaminant, but all salt mixes tested generally the same as
NSW.

Calcium

Iodine (ppm)

Another halogen like Bromine, Iodine is generally not
considered a heavy metal contaminant. All salts except Omega Sea
tested below the 0.5 ppm test detection limit.

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Iodine

Potassium (ppm)

Potassium is a major element in sea water that generally
exists as a free metal ion. All salt mix levels were slightly
below NSW concentrations.

Potassium

Magnesium (ppm)

An essential part of the buffer system, Magnesium levels were
generally similar to NSW for all salt mixes.

Magnesium

Sodium (ppm)

Sodium is the second most common element in sea water, after
Chlorine. All salt mixes were slightly below NSW levels.

Sodium

Rubidium (ppb)

Rubidium is potentially a heavy metal toxin, but all salt
mixes were well below NSW levels.

Rubidium

Sulfur (ppm)

Sulfur exists in sea water primarily as Sulfate ions. All salt
mixes had similar Sulfur levels, well below NSW levels.

Sulfur

Vanadium (ppb)

Vanadium is another heavy metal that was reported in Dr.
Shimek’s study to be significantly higher in Instant Ocean
and Coralife than in Crystal Sea Bio-Assay. Our results indicate
that Crystal Sea Bio-Assay is comparable to Instant Ocean, and
that Bio-Sea MarineMix measures the highest.

Vanadium

1 “This study has demonstrated
that the artificial sea water made using some common and
popular commercial artificial salt water mixes is toxic to
sea urchin larvae using a variant of a standard bioassay.
Such water will also likely have effects on other
animals.” Shimek, 2003

2 “This study also showed that
some artificial sea water mixes produced water that could
support larval development as well as could natural
seawater.” Shimek, 2003

3 “The two salts that made
artificial seawater with the lowest survivorship of larvae
consistently have heavy metals concentrations hundreds to
hundreds of thousands times those found in natural
seawater. Those salts that had the best survival had heavy
metals concentrations that generally ranged about from, at
worst, about one third to, at best, one thousandth those
values.” Shimek, 2003

4 “… I had to rely on data
provided by the manufacturer of Crystal Sea Marinemix
Bioassay Formula. For the Bio-Sea Marinemix, I used the
data from one of the advertising brochures describing the
salt.” Shimek, 2003

5 “Fortunately, there is no
a priori reason to doubt the veracity of either
of these sources.” Shimek, 2003

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 Mathew Marulla

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