Synthetic sea water solution kit and method of manufacture

A concentrated, synthetic, sea water solution; which upon dilution with fresh water produces a high purity, synthetic sea water and a method for making the same. The liquid mixture is composed of two, separate and equal volume, portions; each portion containing a percentage of specific major and minor ions. The solution may also contain essential trace elements. The solution is extremely pure; being specifically treated to remove harmful, non-essential, heavy metals.

BACKGROUND--FIELD OF INVENTION 
This invention relates to the production and composition of an artificial 
sea water solution, specifically to a concentrated, high purity solution. 
BACKGROUND--DESCRIPTION OF PRIOR ART 
Efforts to create an artificial solution of sea water for the maintenance 
of marine life are recorded as early as 1854 by Gosse. However natural sea 
water is a complex mixture of organic and inorganic compounds and only 
recently have attempts to formulate suitable substitutes proved 
successful. 
Gosse and others of the period used only the four major salts naturally 
occurring in sea water to formulate their mixtures and met with only 
limited success. They rightly surmised something was missing and so began 
inoculating their mixtures with seaweed or some living organism. This 
improved the environment, however their success in maintaining organisms 
for long periods of time was still limited. 
There were two primary reasons for the shortcomings of these initial 
attempts; a failure to understand the complexity of natural sea water and 
a lack of knowledge of the physiology of marine fish and invertebrates. 
As chemical test instruments and test methods have become increasingly 
sensitive, it has become apparent, natural sea water most likely contains 
every naturally occurring element present on earth. In water, these 
elements are dissolved and lose or gain electrons to form ions. Some 
elements join together to from complex ions. Of all the ions in sea water, 
six are considered major. They are essential to life for the marine 
organism. Five additional ions are termed minor ions. They occur at lower 
concentrations than the six major ions and their importance to marine 
organisms is less well understood. The balance of the elements found in 
natural sea water are termed as trace elements and only fourteen of them 
are considered to be essential. (See Table 1., Inorganic Composition of 
Sea Water). The remaining elements are considered at this time to be 
nonessential. It is also well known that an excess of any element or ion 
can prove fatal to the marine organisms involved, whether captive or in a 
natural state. 
Most modern, commercial mixtures for sea salts utilize this now well 
documented relationship of major and minor elements in natural sea water. 
Some manufacturers of synthetic sea salts also add additional trace 
elements to their formulations. When properly mixed and as long as overall 
water quality is maintained, they are quite capable of sustaining marine 
life for perhaps as long as those organisms would normally live in their 
native environment. Problems arise when these salts are not properly 
utilized or when the water quality is allowed to deteriorate to a point at 
which the organisms are poisoned. 
Obviously no manufacturer of sea salt mixtures can be responsible for the 
way the consumer uses the product. The manufacturer must make the product 
as easy to use as possible and provide clear, easy to follow instructions. 
The formulation of the sea salt must also be as pure as possible and all 
elements balanced as closely as possible with regard to naturally 
occurring sea water. This optimum formulation is more forgiving for the 
major and minor elements and more critical for the trace elements 
including those that are essential. The reason being is at optimum pH, 
most of the trace elements are chelated by various anions in the solution 
(sulfates, phosphates, carbonates, hydroxides, etc.) and are not capable 
of causing distress to the organisms in the system. However, should the pH 
drop and the water become more acidic, these elements are released and are 
free to interfere with the organism's metabolism. This is an extremely 
dangerous condition and should be avoided. 
Since the pH in a closed system always tends to lower over time, the sea 
salt mixture should not contain an excess of trace elements. This is not 
easily guaranteed because, in its natural state, sodium chloride, the 
major constituent in sea water, contains many trace elements. The number 
of trace elements and amounts thereof vary greatly dependent from where 
the sodium chloride was mined. Using sodium chloride in its natural 
condition (rock salt) to formulate a synthetic sea salt mixture would most 
likely be toxic to the marine organisms it was designed to sustain. Since 
it is not economically practical to use a highly purified or reagent grade 
of salt, most commercial formulations rely on a technical grade of sodium 
chloride as well as the other salts which compose sea water. The most pure 
of these salts typically contain a minimum of five parts per million total 
metallic impurities. Depending on the impurities present, (copper, lead, 
arsenic, mercury, iron) this amount can be enough to poison the organisms 
present should the pH be allowed to drop to unacceptable levels. 
Dry, commercially available salts are also cumbersome to use. A mixing 
container separate from the aquarium must be used. The salts dissolve 
slowly, require much stirring and then must be allowed to settle, 
preferably over night before addition to the system. 
Presently available salts also tend to form insoluble precipitates during 
storage and upon mixing. U.S. Pat. Nos. 3,623,455 (1971), 3,886,904 (1973) 
and 3,585,967 (1971) all discuss and suggest various solutions to 
eliminate such problems. In U.S. Pat. Nos. 3,623,455 and 3,585,967 to 
Kelley et al., the inventors propose rising salts with carefully 
controlled moisture contents, but then admit the formulation will still 
form a slight precipitate when dissolved. In U.S. Pat. No. 3,886,904 to 
King and in U.S. Pat. No. 3,585,967 to Kelly, a two part mixture is 
utilized. One part is a blend of dry salts, the second part is a liquid 
containing dissolved trace elements. This solves the problem of trace 
element solubility, but does nothing to eliminate the properties of the 
dry salts to absorb moisture and form insoluble precipitates. 
Furthermore, none of the available commercial salts, nor any previously 
patented mixtures or blends of salts, solve the most inconvenient property 
of all such products. All the chemical salts used to Formulate these 
mixtures are hygroscopic (water attracting) to varying degrees. (Calcium 
chloride is so hygroscopic it has been used to dehumidify damp air.) 
Therefore once the package containing these salt blends has been opened, 
it is extremely difficult to reseal it tight enough to prevent the mixture 
from absorbing water and hardening. Even in unopened packages the salt 
mixtures tend to solidify in time. 
OBJECTS AND ADVANTAGES 
Accordingly, several objects and advantages of the present invention are: 
(a) to provide a sea salt concentrate which will yield a synthetic sea 
water solution capable of sustaining any and all types of marine organisms 
for an indefinite period of time; 
(b) to provide a sea salt concentrate which does not contain an excess of 
any element, particularly those elements which are neither major or minor 
elements, but which are considered trace elements; 
(c) to provide a sea salt concentrate which is easily mixed; 
(d) to provide a sea salt concentrate which is not hygroscopic and will not 
harden upon aging; 
(e) to provide a sea salt concentrate which does not form insoluble 
precipitates; 
(f) to provide a sea salt concentrate which, after mixing, is not required 
to age for any period of time before addition to the marine environment 
(aquarium); and 
(g) to provide a sea salt concentrate which in small volumes, can be added 
directly to the aquarium. 
Further objects and advantages are to provide an economical sea salt 
concentrate which is easy and convenient to use and store and which, when 
properly mixed, will not contain any metallic elements in high enough 
concentrations to adversely affect the health of the marine environment 
should the pH of the system be allowed to drop.

DESCRIPTION 
A typical embodiment of my synthetic sea water solution is as shown in 
TABLE 2. The solution concentrate is composed of two equal, liquid 
portions; Pan A and Part B. The concentrated solution is a ten times 
concentrate. This is readily seen by comparing the amounts of major and 
minor ions listed in TABLE 1. 
The advantages gained by utilizing a concentrated, two-part mixture are 
considerable. The salts that would normally form insoluble precipitates 
are now separated. The amount of time the product can be stored, its 
shelf-life, is virtually unlimited. Also, since the salts have already 
been dissolved in water, mixing is quick and simple. Aging after mixing is 
eliminated and no precipitates will be formed provided the simple mixing 
directions are followed. Further, a ten-times concentrate saves volume in 
transport and storage. 
Another major advantage for utilizing a liquid concentrate can best be 
illustrated by TABLE 3; a List of Metal Ions Precipitated by Sulfide, and 
TABLE 3, Solubility Product Constants of Some Metallic Sulfides. As can be 
seen, most of the heavy metallic ions are precipitated by sulfide. 
Referring to Table 3, note the extremely small solubility product 
constants for some of the more common metallic sulfides. The smaller the 
solubility product, the less soluble (more insoluble) the sulfide of the 
corresponding metal. For example: mercury (II) sulfide has a solubility 
product of 2.0.times.10.sup.-53 whereas the solubility product of copper 
(I) sulfide is 2.26.times.10.sup.-48. This means that mercurous sulfide is 
approximately one hundred thousand times less soluble than cuprous 
sulfide. The most important aspect of the solubility of the metallic 
sulfides for this discussion, is the fact they are all extremely 
insoluble. A solubility of 1.times.10.sup.-9 means only 1 gram of material 
can dissolve in one billion liters of water. 
Since all of the commonly used salts in the manufacture of sea water 
mixtures contain metallic impurities, a method by which the resulting 
mixture can be easily purified is highly desirable. By dissolving the 
major salts in their proper proportions and treating the resultant 
solution with a source of sulfur, such as hydrogen sulfide gas, virtually 
all heavy metal contaminants will be precipitated. These precipitates are 
then filtered out and the excess hydrogen sulfide is driven off. The 
liquid concentrates, Part A and Part B, now contain only the desired major 
and minor elements. At this point, the correct amounts of the essential 
trace elements are returned to the mixture. 
This method of purification produces a sea water mixture which will not 
release harmful amounts of trace elements should the pH of the 
aqua-culture environment be allowed to drop. 
OPERATION 
The manner of using my synthetic sea water concentrate, while simple, 
differs considerably from that of the mixtures presently available. 
The first step is to determine what volume of sea water is required and 
remove it from the system. The amount of Part A and Part B together, will 
be equal to one tenth of this volume. For example, a marine aquarium of 
4000 liters needs a 10% water change. Therefore, the amount of fresh sea 
water required is 400 liters. Of this 400 liters, 40 liters will consist 
of my synthetic sea water concentrate. The 40 liters of concentrate will 
be divided equally between Parts A and B, 20 liters of each. 
After the 400 liters has been removed from the system, 20 liters of Part A 
are accurately measured and added to an adequately sized mixing vessel. 
Next, 360 liters (90% of the 400 required) of fresh water (preferably 
deionized or distilled) is added. The remaining 20 liters of Part B are 
added last. The mixture may be stirred if desired, although the agitation 
resulting from pouring the solutions together and pumping or pouring the 
final solution into the aquarium is usually sufficient. 
Additions to an existing system of 10% of total volume or less, can be made 
directly to the aquarium if desired. Also, the make-up of the total volume 
of sea water for a new system can be accomplished directly in the 
aquarium. TABLE 4, Table of Make-Up, shows several examples as well as a 
general formula for calculating the correct amounts of Pans A, B and 
distilled water, to make up any required amount of sea water. 
SUMMARY, RAMIFICATIONS, SCOPE 
Accordingly, the reader can see the synthetic, sea water concentrate of 
this invention can be used to quickly and conveniently produce a salt 
water solution which contains the proper amounts of all major and minor 
elements as well as the necessary trace elements without containing 
potentially hazardous amounts of any heavy metal impurities. In addition, 
this invention eliminates several problems which are common to previous 
inventions of synthetic sea salt mixtures in that 
it provides a method to make additions of up to 10% directly to the marine 
environment; 
it prohibits the formation of insoluble precipitates upon mixing; 
it provides a solution which requires no aging period before its addition 
to the system; 
it provides a sea salt concentrate which will not harden in the container 
during storage; 
it provides a salt water concentrate which, in the case of a new 
environment, can be used to make up, directly in the aquarium, tank, etc., 
a synthetic sea water, immediately before the addition of the marine 
organisms. 
Although the description contains many specifics, these should not be 
construed as limiting the scope of this invention, but rather as merely 
providing examples of some of the preferred embodiments of this invention. 
For example: the liquid concentrates, Parts A and B, could be blended as 
six or eight times concentrates; different salts could be used as sources 
for the various elements; the division of salts and/or elements could vary 
between Parts A and B; a different source of sulfur from hydrogen sulfide 
could be used to precipitate the heavy metals in the preparation of the 
concentrate; the number of parts of the concentrated mixture could be 
increased to three, etc. 
Thus the scope of the invention should be determined by the appended claims 
and their legal equivalents, rather than the examples given. 
TABLE 1 
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INORGANIC COMPOSITION OF SEA WATER.sup.1 
Component Concentration (mg/l) 
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MAJOR IONS 
Chloride 19,000 
Sodium 10,500 
Sulfate 2,600 
Magnesium 1,350 
Calcium 400 
Potassium 380 
MINOR IONS 
Bicarbonate 142 
Bromide 65 
Borate 25 
Strontium 8 
Silicate 8 
TRACE ELEMENTS 
Aluminum 0.01 
Arsenic 0.003 
Barium 0.03 
Cadmium 0.0001 
Cesium 0.0003 
Chromium.sup.2 0.00005 
Cobalt.sup.2 0.0004 
Copper.sup.2 0.003 
Fluorine.sup.2 1.2 
Iodine.sup.2 0.06 
Iron.sup.2 0.01 
Lead 0.00003 
Lithium 0.17 
Manganese.sup.2 0.002 
Mercury 0.0002 
Molybdenum.sup.2 
0.01 
Nickel.sup.2 0.007 
Phosphorous.sup.2 
0.07 
Rubidium 0.12 
Selenium.sup.2 0.0001 
Tin.sup.2 0.001 
Thorium 0.000001 
Titanium 0.001 
Uranium 0.003 
Vanadium.sup.2 0.002 
Zinc.sup.2 0.01 
Total of all others 
Less than 0.10 
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.sup.1 Typical analysis, composition may vary by location. 
.sup.2 Considered to be an essential trace element. 
References: 
S. Spotte, Captive Seawater Fishes: Science and Technology, John Wiley & 
Sons, Inc., New York, 1992, ISBN 0471-54554-6. 
E. Mowka, The SeaWater Manual, Aquarium Systems, Ohio, 1981. 
TABLE 2 
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Major and Minor Ions 
Ion Part A (mg/l) 
Part B (mg/l) 
Total (mg/l) 
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COMPOSITION OF CONCENTRATE.sup.1 
Chloride 89,200 99,800 189,000 
Sodium 52,600 52,100 104,700 
Sulfate 25,350 25,350 
Magnesium 
9,450 3,000 12,450 
Calcium 4,000 4,000 
Potassium 
50 3,950 4,000 
Bicarbonate 
1,450 1,450 
Bromide 600 600 
Borate 250 250 
Strontium 100 100 
Silicate 80 80 
COMPOSITON OF DILUTED CONCENTRATE 
Chloride 8,920 9,980 18,900 
Sodium 5,260 5,210 10,470 
Sulfate 2,535 2,535 
Magnesium 
945 300 1,245 
Calcium 400 400 
Potassium 
5 395 400 
Bicarbonate 
145 145 
Bromide 60 60 
Borate 25 25 
Strontium 10 10 
Silicate 8 8 
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.sup. 1 Typical analysis, composition may vary slighty from batch to 
batch. 
TABLE 3 
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LIST OF METAL IONS 
PRECIPITATED BY SULFIDE AT pH 7 
Ag.sup.+1 Os.sup.+4 
As.sup.+3 Pb.sup.+2 
Au.sup.+3 Pd.sup.+2 
Bi.sup.+3 Pt.sup.+2 
Cd.sup.+2 Re.sup.+4 
Co.sup.+2 Rh.sup.+2 
Cr.sup.+3 Ru.sup.+4 
Fe.sup.+2 Sb.sup.+3 
Ge.sup.+2 Se.sup.+2 
Hg.sup.+2 Sn.sup.+2 
In.sup.+3 Te.sup.+4 
Ir.sup.+4 Tl.sup.+1 
Mn.sup.+2 V.sup.+4 
Mo.sup.+3 Zn.sup.+2 
Ni.sup.+2 
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SOLUBILITY PRODUCT 
CONSTANTS OF SOME METALLIC SULFIDES 
Bismuth Sulfide Bi.sub.2 S3 
1.82 .times. 10.sup.-99 
Cadmium Sulfide CdS 1.40 .times. 10.sup.-29 
Copper(I) Sulfide Cu.sub.2 S 
2.26 .times. 10.sup.-48 
Copper(II) Sulfide CuS 1.27 .times. 10.sup.-36 
Iron(II) Sulfide FeS 1.59 .times. 10.sup.-19 
Lead Sulfide PbS 9.04 .times. 10.sup.-29 
Manganese(II) Sulfide 
MnS 4.65 .times. 10.sup.-14 
Mercury(II) Sulfide 
HgS 2.00 .times. 10.sup.-53 
Nickel(II) Sulfide NiS 1.07 .times. 10.sup. -21 
Palladium(II) Sulfide 
PdS 2.03 .times. 10.sup.-58 
Platinum(II) Sulfide 
PtS 9.91 .times. 10.sup.-74 
Silver(I)(alpha form) Sulfide 
Ag.sub.2 S 
6.69 .times. 10.sup.-50 
Tin(II) Sulfide SnS 3.25 .times. 10.sup.-28 
Zinc Sulfide ZnS 2.93 .times. 10.sup.-25 
______________________________________ 
Reference: 
J. Snyder, Jr., Editor, Handbook of Chemistry and Physics, 71st Ed., CRC 
Press, Boston, 1990. 
TABLE 4 
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TABLE OF MAKE-UP 
Amount of Amount of Amount of Amount of 
Sea Water Part A Part B Distilled Water 
Liters required 
Liters to use 
Liters to use 
to use (liters) 
______________________________________ 
10 0.5 0.5 9 
20 1.0 1.0 18 
50 2.5 2.5 45 
100 5 5 90 
200 10 10 180 
500 25 25 450 
1000 50 50 900 
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FORMULAE OF MAKE-UP 
1. SW 20 = A 
2. A = B 
3. DW = (A + B) .times. 9 
SW = amount of sea water required in liters 
A = amount of concentrate Part A in liters 
B = amount of concentrate Part B in liters 
DW = amount of distilled water in liters 
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