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Bittern (pl. bitterns), or nigari, is the
salt In common usage, salt is a mineral composed primarily of sodium chloride (NaCl). When used in food, especially in granulated form, it is more formally called table salt. In the form of a natural crystalline mineral, salt is also known as r ...
solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Solu ...
formed when
halite Halite ( ), commonly known as rock salt, is a type of salt, the mineral (natural) form of sodium chloride ( Na Cl). Halite forms isometric crystals. The mineral is typically colorless or white, but may also be light blue, dark blue, purple, pi ...
(table salt) precipitates from
seawater Seawater, or sea water, is water from a sea or ocean. On average, seawater in the world's oceans has a salinity of about 3.5% (35 g/L, 35 ppt, 600 mM). This means that every kilogram (roughly one liter by volume) of seawater has approximat ...
or
brine Brine (or briny water) is a high-concentration solution of salt (typically sodium chloride or calcium chloride) in water. In diverse contexts, ''brine'' may refer to the salt solutions ranging from about 3.5% (a typical concentration of seawat ...
s. Bitterns contain
magnesium Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
,
calcium Calcium is a chemical element; it has symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to it ...
, and
potassium Potassium is a chemical element; it has Symbol (chemistry), symbol K (from Neo-Latin ) and atomic number19. It is a silvery white metal that is soft enough to easily cut with a knife. Potassium metal reacts rapidly with atmospheric oxygen to ...
ions as well as
chloride The term chloride refers to a compound or molecule that contains either a chlorine anion (), which is a negatively charged chlorine atom, or a non-charged chlorine atom covalently bonded to the rest of the molecule by a single bond (). The pr ...
,
sulfate The sulfate or sulphate ion is a polyatomic anion with the empirical formula . Salts, acid derivatives, and peroxides of sulfate are widely used in industry. Sulfates occur widely in everyday life. Sulfates are salts of sulfuric acid and many ...
,
iodide An iodide ion is I−. Compounds with iodine in formal oxidation state −1 are called iodides. In everyday life, iodide is most commonly encountered as a component of iodized salt, which many governments mandate. Worldwide, iodine deficiency ...
, and other ions. Bittern is commonly formed in salt ponds where the
evaporation Evaporation is a type of vaporization that occurs on the Interface (chemistry), surface of a liquid as it changes into the gas phase. A high concentration of the evaporating substance in the surrounding gas significantly slows down evapora ...
of water prompts the precipitation of halite. These salt ponds can be part of a salt-producing industrial facility, or they can be used as a waste storage location for brines produced in
desalination Desalination is a process that removes mineral components from saline water. More generally, desalination is the removal of salts and minerals from a substance. One example is Soil salinity control, soil desalination. This is important for agric ...
processes. Bittern is a source of many useful salts. It is used as a natural source of Mg2+, and it can be used as a coagulant both in the production of
tofu or bean curd is a food prepared by Coagulation (milk), coagulating soy milk and then pressing the resulting curds into solid white blocks of varying softness: ''silken'', ''soft'', ''firm'', and ''extra (or super) firm''. It originated in Chin ...
and in the treatment of
industrial wastewater Industrial wastewater treatment describes the processes used for treating wastewater that is produced by industries as an undesirable by-product. After treatment, the treated industrial wastewater (or effluent) may be reused or released to a s ...
.


History

Bittern has been extracted for a long time, at least several centuries. The Dutch chemist Petrus Jacobus Kipp (1808–1864) experimented with saturated solutions of bittern. The term for the solution is a modification of "bitter".


Uses


Salt derivation

Bittern is a source of many salts including
magnesium sulfate Magnesium sulfate or magnesium sulphate is a chemical compound, a salt with the formula , consisting of magnesium cations (20.19% by mass) and sulfate anions . It is a white crystalline solid, soluble in water but not in ethanol. Magnesi ...
(epsom salt). Multiple methods exist for removing these salts from the bittern, and the method ultimately used depends on the target product. Products that would naturally precipitate from the bitterns crystallize as
evaporation Evaporation is a type of vaporization that occurs on the Interface (chemistry), surface of a liquid as it changes into the gas phase. A high concentration of the evaporating substance in the surrounding gas significantly slows down evapora ...
proceeds (e. g.
kainite Kainite ( or ) (KMg(SO4)Cl·3H2O) is an evaporite mineral in the class of "Sulfates (selenates, etc.) with additional anions, with H2O" according to the Nickel–Strunz classification. It is a hydrated potassium-magnesium sulfate-chloride, natu ...
). Products that do not preferentially precipitate from bitterns may precipitate through the addition of another compound or through
ion exchange Ion exchange is a reversible interchange of one species of ion present in an insoluble solid with another of like charge present in a solution surrounding the solid. Ion exchange is used in softening or demineralizing of water, purification of ch ...
. Potassium-magnesium sulfate double salt, a good
fertilizer A fertilizer or fertiliser is any material of natural or synthetic origin that is applied to soil or to plant tissues to supply plant nutrients. Fertilizers may be distinct from liming materials or other non-nutrient soil amendments. Man ...
, is a salt that precipitates from bitterns upon addition of
methanol Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical compound and the simplest aliphatic Alcohol (chemistry), alcohol, with the chemical formula (a methyl group linked to a hydroxyl group, often ab ...
.
Ethanol Ethanol (also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound with the chemical formula . It is an Alcohol (chemistry), alcohol, with its formula also written as , or EtOH, where Et is the ps ...
is also used, but it exhibits a preference for
potassium sulfate Potassium sulfate (US) or potassium sulphate (UK), also called sulphate of potash (SOP), arcanite, or archaically potash of sulfur, is the inorganic compound with formula K2SO4, a white water-soluble solid. It is commonly used in fertilizers, prov ...
precipitation. The solution can furthermore be used in the production of
potash Potash ( ) includes various mined and manufactured salts that contain potassium in water- soluble form.
and potassium salts.
Tartaric acid Tartaric acid is a white, crystalline organic acid that occurs naturally in many fruits, most notably in grapes but also in tamarinds, bananas, avocados, and citrus. Its salt (chemistry), salt, potassium bitartrate, commonly known as cream of ta ...
is one compound that can facilitate the precipitation of these salts.
Magnesium hydroxide Magnesium hydroxide is an inorganic compound with the chemical formula Mg(OH)2. It occurs in nature as the mineral brucite. It is a white solid with low solubility in water (). Magnesium hydroxide is a common component of antacids, such as milk o ...
(Mg(OH)2) can be derived from bittern. Adding an
alkali In chemistry, an alkali (; from the Arabic word , ) is a basic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a soluble base has a pH greater than 7.0. The a ...
ne
solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Solu ...
such as
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...
(NaOH) or lime will cause magnesium hydroxide to precipitate, although lime is not as effective. Slower addition of the alkaline solution results in the precipitation of larger particles that are easier to remove from solution.


Coagulation


Tofu

Nigari is produced from seawater after first removing
sodium chloride Sodium chloride , commonly known as Salt#Edible salt, edible salt, is an ionic compound with the chemical formula NaCl, representing a 1:1 ratio of sodium and chloride ions. It is transparent or translucent, brittle, hygroscopic, and occurs a ...
. It contains mostly
magnesium chloride Magnesium chloride is an inorganic compound with the formula . It forms hydrates , where ''n'' can range from 1 to 12. These salts are colorless or white solids that are highly soluble in water. These compounds and their solutions, both of which ...
, smaller amounts of
magnesium sulfate Magnesium sulfate or magnesium sulphate is a chemical compound, a salt with the formula , consisting of magnesium cations (20.19% by mass) and sulfate anions . It is a white crystalline solid, soluble in water but not in ethanol. Magnesi ...
(Epsom salt),
potassium chloride Potassium chloride (KCl, or potassium salt) is a metal halide salt composed of potassium and chlorine. It is odorless and has a white or colorless vitreous crystal appearance. The solid dissolves readily in water, and its solutions have a sa ...
,
calcium chloride Calcium chloride is an inorganic compound, a Salt (chemistry), salt with the chemical formula . It is a white crystalline solid at room temperature, and it is highly soluble in water. It can be created by neutralising hydrochloric acid with cal ...
, and trace amounts of other naturally occurring salts. Nigari was the first coagulant used to make
tofu or bean curd is a food prepared by Coagulation (milk), coagulating soy milk and then pressing the resulting curds into solid white blocks of varying softness: ''silken'', ''soft'', ''firm'', and ''extra (or super) firm''. It originated in Chin ...
in Japan. It is still used today because tofu made using bittern preserves the original flavor of the
soybean The soybean, soy bean, or soya bean (''Glycine max'') is a species of legume native to East Asia, widely grown for its edible bean. Soy is a staple crop, the world's most grown legume, and an important animal feed. Soy is a key source o ...
s used to make it. Bittern causes rapid coagulation which influences the quality of the tofu. Alternatively
calcium sulfate Calcium sulfate (or calcium sulphate) is an inorganic salt with the chemical formula . It occurs in several hydrated forms; the anhydrous state (known as anhydrite) is a white crystalline solid often found in evaporite deposits. Its dihydrate ...
,
calcium chloride Calcium chloride is an inorganic compound, a Salt (chemistry), salt with the chemical formula . It is a white crystalline solid at room temperature, and it is highly soluble in water. It can be created by neutralising hydrochloric acid with cal ...
or other substances are also used.


Wastewater treatment

Bittern can be used instead of
aluminum Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
-based coagulants in the treatment of wastewater produced during the fabric-
dyeing Dyeing is the application of dyes or pigments on textile materials such as fibers, yarns, and fabrics with the goal of achieving color with desired color fastness. Dyeing is normally done in a special solution containing dyes and particular ...
process. The wastewater pH is
basic Basic or BASIC may refer to: Science and technology * BASIC, a computer programming language * Basic (chemistry), having the properties of a base * Basic access authentication, in HTTP Entertainment * Basic (film), ''Basic'' (film), a 2003 film ...
, which is favorable for the use of bittern. After the addition of bittern, precipitated magnesium hydroxide works as the coagulant to collect
dye Juan de Guillebon, better known by his stage name DyE, is a French musician. He is known for the music video of the single "Fantasy Fantasy is a genre of speculative fiction that involves supernatural or Magic (supernatural), magical ele ...
, solids,
organic matter Organic matter, organic material or natural organic matter is the large source of carbon-based compounds found within natural and engineered, terrestrial, and aquatic environments. It is matter composed of organic compounds that have come fro ...
, and
heavy metals upright=1.2, Crystals of lead.html" ;"title="osmium, a heavy metal nearly twice as dense as lead">osmium, a heavy metal nearly twice as dense as lead Heavy metals is a controversial and ambiguous term for metallic elements with relatively h ...
from the wastewater before settling out of solution. The
sludge Sludge (possibly , or some dialect related to slush) is a semi-solid slurry that can be produced from a range of industrial processes, from water treatment, wastewater treatment or on-site sanitation systems. It can be produced as a settled sus ...
produced from this wastewater treatment is also easier to dispose of than sludge produced by aluminum-based coagulants because there are less restrictions surrounding the disposal of magnesium, and it may be possible to recycle the sludge as fertilizer. Bittern can also be used as a source of magnesium ions (Mg2+) for the precipitation of struvite, a useful fertilizer, from wastewater containing
nitrogen Nitrogen is a chemical element; it has Symbol (chemistry), symbol N and atomic number 7. Nitrogen is a Nonmetal (chemistry), nonmetal and the lightest member of pnictogen, group 15 of the periodic table, often called the Pnictogen, pnictogens. ...
and
phosphorus Phosphorus is a chemical element; it has Chemical symbol, symbol P and atomic number 15. All elemental forms of phosphorus are highly Reactivity (chemistry), reactive and are therefore never found in nature. They can nevertheless be prepared ar ...
. One source of useful wastewater is
landfill A landfill is a site for the disposal of waste materials. It is the oldest and most common form of waste disposal, although the systematic burial of waste with daily, intermediate and final covers only began in the 1940s. In the past, waste was ...
leachate A leachate is any liquid that, in the course of passing through matter, extracts soluble or suspended solids, or any other component of the material through which it has passed. Leachate is a widely used term in the environmental sciences wh ...
. Bittern is just as good as other sources of magnesium ions at removing phosphorus from wastewater streams, but it lags behind other magnesium ion sources in terms of the removal of
ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...
(a nitrogen compound).


Other uses

Bittern can be used to culture '' Haloquadratum''
archaea Archaea ( ) is a Domain (biology), domain of organisms. Traditionally, Archaea only included its Prokaryote, prokaryotic members, but this has since been found to be paraphyletic, as eukaryotes are known to have evolved from archaea. Even thou ...
. ''Haloquadratum'' are distinctly square-shaped and are abundant in hypersaline environments such as salt ponds. Their cultivation is necessary for understanding both their
ecological Ecology () is the natural science of the relationships among living organisms and their environment. Ecology considers organisms at the individual, population, community, ecosystem, and biosphere levels. Ecology overlaps with the closely re ...
function in those environments as well as their unique
morphology Morphology, from the Greek and meaning "study of shape", may refer to: Disciplines *Morphology (archaeology), study of the shapes or forms of artifacts *Morphology (astronomy), study of the shape of astronomical objects such as nebulae, galaxies, ...
. The presence of ''Haloquadratum'' in an environment deemed inhospitable for most life has prompted closer study of these archaea. A study has been performed exploring the use of bittern as a natural magnesium supplement used to decrease cholesterol spikes after a meal (postprandial
hyperlipidemia Hyperlipidemia is abnormally high levels of any or all lipids (e.g. fats, triglycerides, cholesterol, phospholipids) or lipoproteins in the blood. citing: and The term ''hyperlipidemia'' refers to the laboratory finding itself and is also use ...
). Due to its high salinity, bittern can also be used as a draw solution for an osmotic process that concentrates
sucrose Sucrose, a disaccharide, is a sugar composed of glucose and fructose subunits. It is produced naturally in plants and is the main constituent of white sugar. It has the molecular formula . For human consumption, sucrose is extracted and refined ...
in
sugarcane Sugarcane or sugar cane is a species of tall, Perennial plant, perennial grass (in the genus ''Saccharum'', tribe Andropogoneae) that is used for sugar Sugar industry, production. The plants are 2–6 m (6–20 ft) tall with stout, jointed, fib ...
juice. Because forward osmosis is being used, the process is relatively energy-efficient. Epsom salt can also be taken from the bittern draw solution once it is used. This method is particularly useful in areas where sugarcane and salt production are in close proximity to avoid costs associated with movement of either the sugarcane juice or the bittern.


Environmental impact

In some jurisdictions, most bitterns are used for other production instead of being directly discarded. In other jurisdictions each tonne of salt produced can create 3+ tonnes of waste bitterns. Although bittern generally contains the same compounds as seawater, it is much more concentrated than seawater. If bittern is released directly into seawater, the ensuing
salinity Salinity () is the saltiness or amount of salt (chemistry), salt dissolved in a body of water, called saline water (see also soil salinity). It is usually measured in g/L or g/kg (grams of salt per liter/kilogram of water; the latter is dimensio ...
increase may harm
marine life Marine life, sea life or ocean life is the collective ecological communities that encompass all aquatic animals, aquatic plant, plants, algae, marine fungi, fungi, marine protists, protists, single-celled marine microorganisms, microorganisms ...
around the point of release. Even small increases in salinity can disrupt marine species' osmotic balances, which may result in the death of the
organism An organism is any life, living thing that functions as an individual. Such a definition raises more problems than it solves, not least because the concept of an individual is also difficult. Many criteria, few of them widely accepted, have be ...
in some cases. In December 1997, 94 corpses of green sea turtles, '' Chelonia mydas'', were found at the Ojo de Liebre Lagoon (OLL) in Mexico, adjacent to the industrial operation of Exportadora de Sal S.A. (ESSA), the largest saltworks in the world. The fluoride ion F content in bitterns was 60.5-fold more than that in seawater. The bitterns osmolality was 11,000 mosm/kg of water, whereas the turtle's plasma osmolality was about 400 mosm/kg of water. Researchers concluded that the dumping of bitterns into the ocean should be avoided. The lack of adequate disposal methods for bitterns and concerns of local commercial and recreational fishing associations about bitterns’ deleterious impacts upon local fish and prawn hatchery areas led the Western Australian EPA in 2008 to recommend against the proposed 4.2 million tonne per annum Straits Salt project in The Pilbara region of WA. The EPA concluded that:


References

{{Salt topics Salts Chemistry Evaporite