The Carbonates Class

Including the Carbonates, the Uranyl Carbonates , the Rare Earth Carbonates, the Nitrates, the Iodates and the Borates. The carbonates and related nitrates and borates are common constituents of the earth's near-surface crust. This is a structurally-related as well as chemically-related group The basic anionic (negatively charged) unit of this class consists of a triangle where at the center resides either a carbon, nitrogen or boron atom. At every corner of the triangle sits an oxygen atom. The threefold symmetry of the triangle explains the trigonal symmetry that many members of this class possess. As long as the triangles of the anionic group fall in a plane parallel with the plane of the triangle and all other bonds in the structure, when viewed perpendicular to this plane, are multiples of three, and are evenly separated from each other, the mineral will have a trigonal symmetry. As complicated as this seems it is in fact the simplest condition of the carbonates. Simplicity often expresses the highest symmetry. As a sphere is more symmetrical than a football; a simple carbonate is more symmetrical than a more complex carbonate and in fact has the highest symmetry of this class, bar 3 2/m. Although somewhat varied, this class' properties can be generalized more so than the other classes. Typical carbonates are transparent, lightly colored with a white streak, average to above average in density, soft with good to perfect cleavage, soluble to at least some degree in acidic solutions, and tend to originate in sedimentary and oxidizing environments with the exception of carbonatite igneous intrusions. Most of these common characteristics are due to the common chemistry the group shares and members that diverge from the norm do so because of the effects of metal cations such as lead, copper, manganese and iron. The Borate minerals as a whole are more complex in their structures than typical carbonates and could be considered their own class for that reason. For more discussion and a rather extensive list of borate minerals see the Borate Minerals page.

The Mineral CALCITE

Chemistry: CaCO3, Calcium Carbonate Class: Carbonates

Group: Calcite Uses: In cements and mortars, production of lime, limestone is used in the steel industry; glass industry, ornamental stone, chemical and optical uses and as mineral specimens. Calcite's Physical Properties Specimens

Calcite, which gets its name from "chalix" the Greek word for lime, is a most amazing and yet, most common mineral. It is one of the most common minerals on the face of the Earth, comprising about 4% by weight of the Earth's crust and is formed in many different geological environments. Calcite can form rocks of considerable mass and constitutes a significant part of all three major rock classification types. It forms oolitic, fossiliferous and massive limestones in sedimentary environments and even serves as the cements for many sandstones and shales. Limestone becomes marble from the heat and pressure of metamorphic events. Calcite is even a major component in the igneous rock called carbonatite and forms the major portion of many hydrothermal veins. Some of these rock types are composed of better than 99% calcite. Why would a collector be interested in such a common mineral? Because of its extraordinary diversity and beauty! With calcite so abundant and so widely distributed it is no wonder that it can be so varied. The crystals of calcite can form literally a thousand different shapes by combining the basic forms of the positive rhombohedron, negative rhombohedron, steeply, moderately and slightly inclined rhombohedrons, various scalahedrons, prism and pinacoid to name a few of the more common forms. There are more than 300 crystal forms identified in calcite and these forms can combine to produce the thousand different crystal variations. Calcite also produces many twin varieties that are favorites among twin collectors. There are also phantoms, included crystals, color varieties, pseudomorphs and unique associations. There simply is no end to the varieties of calcite. There are several varieties of calcite and it would be impossible to describe them all. However there are a few standouts. Possibly the most well known of calcite's varieties is its most common form, the classic scalenohedron or "Dogtooth Spar" as it is sometimes called. This variety appears as a double pyramid or dipyramid, but is actually a distinctly different form. The point of the scalenohedron is sharp and resembles the canine tooth of a dog, hence the name. Beautiful clear colorless or amber-orange examples of this variety are considered classics and outstanding examples come from Pugh Quarry, Ohio; Cornwall, England and Elmwood, Tennessee but the variety is found worldwide. Not necessarily a variety of calcite, cave formations are certainly a unique aspect of calcite's story. Calcite is the primary mineral component in cave formations. Stalactites and stalagmites, cave veils, cave pearls, "soda straws" and the many other different cave formations that millions of visitors to underground caverns enjoy are made of calcite. It is the fact that calcite is readily dissolved that these formations occur. Overlying limestones or marbles are dissolved away by years and years of slightly acidic ground water to percolate into the caverns below. In fact the caverns themselves may have been the result of water dissolving away the calcite rich rock. As the calcite enriched water enters a

relatively dry cavern, the water starts to evaporate and thus precipitate the calcite. The resulting accumulations of calcite are generally extremely pure and are colored if at all, by very small amounts of iron or other impurities. Mexican onyx is a variety of calcite that is used extensively for ornamental purposes. It is carved into figurines and is so popular that almost every child in the USA owns a small onyx animal or two. Carvings such as vases, bookends, plates, eggs, obilisks, pyramids and statues are all popular. It is not the same onyx as the quartz variety of onyx which is a little more precious (it is used in jewelry) and is banded white and black. To avoid confusion it is best to refer to it as Mexican Onyx. Mexican onyx is banded with multiple orange, yellow, red, tan, brown and white colors that have marble-like texture. The carvings are quite attractive and affordable; a rare combination! Another variety is the so called "Iceland Spar", which is basically clear cleaved fragments of completely colorless (ice-like) calcite. Originally discovered and named after Eskifjord, Iceland where the calcite is found in basalt cavities. In rock shops around the world, iceland spar is available in large quantities and at affordable prices and are popular among children. Most of today's iceland spar comes from Mexico. The iceland spar displays the classic cleavage form of calcite, the rhombohedron. Iceland spar was and is used for optical equipment and during World War II it was a strategic mineral as it was used for the sighting equipment of bombardiers and gunners. It is iceland spar that best demonstrates the unique property of calcite called double refraction. Double refraction occurs when a ray of light enters the crystal and due to calcite's unique optical properties, the ray is split into fast and slow beams. As these two beams exit the crystal they are bent into two different angles (known as angles of refraction) because the angle is affected by the speed of the beams. A person viewing into the crystal will see two images ... of everything. The best way to view the double refraction is by placing the crystal on a straight line or printed word (the result will be two lines or two words). There is only one direction that the beams are both the same speed and that is parallel to the C-axis or primary trigonal axis. Rotation of the crystal will reveal the direction in the crystal that is parallel to the C-axis when the line or word becomes whole again. By contrast, the direction perpendicular to the C-axis will have the greatest separation. The extremely high index of refraction of calcite that causes the easily seen double refraction is also responsible for the interference colors (pastel rainbow colors) that are seen in calcites that have small fractures. Fluorescence, phosphorescence, thermoluminescence and triboluminescence are other important properties of calcite. Although not all specimens demonstrate these properties, some do quite well and this is diagnostic in some cases. One notable case of fluorescence occurs at Franklin, New Jersey where the massive calcite is enriched in a small amount of manganese and fluoresces a bright red under UV light. Some Mexican iceland spar can fluoresce a nice purple or blue color and unique specimens will even phosphoresce (continue to glow) after the UV source has been removed. Triboluminescence is supposedly a property that should occur in most specimens, but is

not easily demonstrated. It occurs when the specimen is struck or put under pressure; in a dark room the specimen should glow when this happens. The best property of calcite is the acid test. Why? Because calcite always will effervesce (bubble) when even cold weak acids are placed on specimens. Even the cement in sandstones will effervesce assuring the geologist of identification of the cementing mineral. The reason for the bubbling is in the formula below: CaCO3 + 2H(+1) -------> Ca(+2) + H2O + CO2 (a gas) The carbon dioxide gas (CO2) is given off as bubbles and the calcium dissolves in the residual water. Any acid, just about, can produce these results, but dilute hydrochloric acid or vinegar are the two recommended acids for this test. Other carbonates such as dolomite or siderite do not react as easily with these acids as does calcite and this leads to differentiating these somewhat similar minerals more readily. Calcite is intricately tied to carbon dioxide in another way. Since many sea organisms such as corals, algae and diatoms make their shells out of calcite, they pull carbon dioxide from the sea water to accomplish this in a near reverse of the reaction above. This is fortuitous for us, as carbon dioxide has been found to be a green house gas and contributes to the so called "green house gas effect". Environmentally then, calcite is very important and may have been quite important to the successful development of our planet in the past. By pulling carbon dioxide out of the sea water, this biological activity allows more of the carbon dioxide in the air to dissolve in the sea water and thus acts as a carbon dioxide filter for he planet. Environmentalists are now actively engaged in determining if this activity can be increase by human intervention to the point of warding off the "green house gas effect". A significant amount of calcite precipitation in sea water is undoubtedly inorganic, but the exact amount that this contributes is not well known. Calcite and other carbonate minerals are very important minerals in the ocean ecosystems of the world. Calcite is not the only calcium carbonate mineral. There are no less than three minerals or phases of CaCO3. Aragonite and vaterite are polymorphs (latin for "many shapes") with calcite, meaning they all have the same chemistry, but different crystal structures and symmetries. Aragonite is orthorhombic, vaterite is hexagonal and calcite is trigonal. Aragonite is a common mineral, but is vastly out distanced by calcite which is the more stable mineral at most temperatures and pressures and in most environments. Vaterite on the other hand is extremely scarce and rarely seen. Aragonite will over time convert to calcite and calcite pseudomorphs after aragonite are not uncommon. Calcite is truly one of the best collection type minerals. There are lots of interesting forms and varieties as well as colorful and beautiful specimens to collect. It is generally easy to identify using its rhomohedral cleavage, reaction to acid and double refraction and makes for a great classroom example of these properties. If it is not the significant mineral on a specimen, it might be an accessory to other wonderful minerals and only enhancing their

attractiveness. With its many different forms, environments, associations and colors, a collector could never have all possible combinations of calcite covered.

PHYSICAL CHARACTERISTICS OF CALCITE:

Color is extremely variable but generally white or colorless or with light shades of yellow, orange, blue, pink, red, brown, green, black and gray. Occasionally iridescent. Luster is vitreous to resinous to dull in massive forms. Transparency: Crystals are transparent to translucent. Crystal System is trigonal; bar 3 2/m Crystal Habits are extremely variable with almost any trigonal form possible. Common among calcite crystals are the scalenohedron, rhombohedron, hexagonal prism, and pinacoid. Combinations of these and over three hundred other forms can make a multitude of crystal shapes, but always trigonal or pseudo-hexagonal. Twinning is often seen and results in crystals with blocky chevrons, right angled prisms, heart shapes or dipyramidal shapes. A notch in the middle of a doubly terminated scalenohedron is a sure sign of a twinned crystal. lamellar twinning also seen resulting in striated cleavage surfaces. Pseudomorphs after many minerals are known, but easily identified as calcite. Also massive, fibrous, concretionary, stalactitic, nodular, oolitic, stellate, dendritic, granular, layered, etc. etc. Cleavage is perfect in three directions, forming rhombohedrons. Fracture is conchoidal. Hardness is 3 (only on the basal pinacoidal faces, calcite has a hardness of less than 2.5 and can be scratched by a fingernail). Specific Gravity is approximately 2.7 (average) Streak is white. Other Characteristics: refractive indices of 1.49 and 1.66 causing a significant double refraction effect (when a clear crystal is placed on a single line, two lines can then be observed), effervesces easily with dilute acids and may be fluorescent, phosphorescent, thermoluminescence and triboluminescent. Associated Minerals are numerous but include these classic associations: Fluorite, quartz, barite, sphalerite, galena, celestite, sulfur, gold, copper, emerald, apatite, biotite, zeolites, several metal sulfides, other carbonates and borates and many other minerals. Notable Occurrences include Pugh Quarry, Ohio; Rosiclare, Illinois; Franklin, New Jersey; Elmwood, Tennessee; Brush Creek and other Missouri, Wisconsin, Kansas and Oklahoma localities, USA; Andreasburg, Harz Mountains and Saxony, Germany; Brazil; Guanajuato, Mexico; Cornwall, Durham and Lancashire, England; Bombay area of India; Eskifjord, Iceland; many African localities as well as others around the world with their own unique varieties. Best Field Indicators are crystal habit, reaction to acid, abundance, hardness, double refraction and especially cleavage.

DOLOMITE

Chemistry: CaMg(CO3)2, Calcium Magnesium Carbonate Class: Carbonates Group: Dolomite Uses: in some cements, as a source of magnesium and as mineral specimens. Specimens

Dolomite, which is named for the French mineralogist Deodat de Dolomieu, is a common sedimentary rock-forming mineral that can be found in massive beds several hundred feet thick. They are found all over the world and are quite common in sedimentary rock sequences. These rocks are called appropriately enough dolomite or dolomitic limestone. Disputes have arisen as to how these dolomite beds formed and the debate has been called the "Dolomite Problem". Dolomite at present time, does not form on the surface of the earth; yet massive layers of dolomite can be found in ancient rocks. That is quite a problem for sedimentologists who see sandstones, shales and limestones formed today almost before their eyes. Why no dolomite? Well there are no good simple answers, but it appears that dolomite rock is one of the few sedimentary rocks that undergoes a significant mineralogical change after it is deposited. They are originally deposited as calcite/aragonite rich limestones, but during a process call diagenesis the calcite and/or aragonite is altered to dolomite. The process is not metamorphism, but something just short of that. Magnesium rich ground waters that have a significant amount of salinity are probably crucial and warm, tropical near ocean environments are probably the best source of dolomite formation. Dolomite in addition to the sedimentary beds is also found in metamorphic marbles, hydrothermal veins and replacement deposits. Except in its pink, curved crystal habit dolomite is hard to distinguish from its second cousin, calcite.But calcite is far more common and effervesces easily when acid is applied to it. But this is not the case with dolomite which only weakly bubbles with acid and only when the acid is warm or the dolomite is powdered. Dolomite is also slightly harder, denser and never forms scalenohedrons (calcite's most typical habit). Dolomite differs from calcite, CaCO3, in the addition of magnesium ions to make the formula, CaMg(CO3)2. The magnesium ions are not the same size as calcium and the two ions seem incompatible in the same layer. In calcite the structure is composed of alternating layers of carbonate ions, CO3, and calcium ions. In dolomite, the magnesiums occupy one layer by themselves followed by a carbonate layer which is followed by an exclusively calcite layer and so forth. Why the alternating layers? It is probably the significant size difference between calcium and magnesium and it is more stable to group the differing sized ions into same sized layers. Other carbonate minerals that have this alternating layered structure belong to the Dolomite Group. Dolomite is the principle member of the Dolomite Group of minerals which includes ankerite, the only other somewhat common member.

Dolomite forms rhombohedrons as its typical crystal habit. But for some reason, possibly twinning, some crystals curve into saddle-shaped crystals. These crystals represent a unique crystal habit that is well known as classical dolomite. Not all crystals of dolomite are curved and some impressive specimens show well formed, sharp rhombohedrons. The luster of dolomite is unique as well and is probably the best illustration of a pearly luster. The pearl-like effect is best seen on the curved crystals as a sheen of light can sweep across the curved surface. Dolomite can be several different colors, but colorless and white are very common. However it is dolomite's pink color that sets another unique characteristic for dolomite. Crystals of dolomite are well known for their typical beautiful pink color, pearly luster and unusual crystal habit and it is these clusters that make very attractive specimens.

PHYSICAL CHARACTERISTICS:

Color is often pink or pinkish and can be colorless, white, yellow, gray or even brown or black when iron is present in the crystal. Luster is pearly to vitreous to dull. Transparency crystals are transparent to translucent. Crystal System is trigonal; bar 3 Crystal Habits include saddle shaped rhombohedral twins and simple rhombs some with slightly curved faces, also prismatic, massive, granular and rock forming. Never found in scalenohedrons. Cleavage is perfect in three directions forming rhombohedrons. Fracture is conchoidal. Hardness is 3.5-4 Specific Gravity is 2.86 (average) Streak is white. Other Characteristics: Unlike calcite, effervesces weakly with warm acid or when first powdered with cold HCl. Associated Minerals: include calcite, sulfide ore minerals, fluorite, barite, quartz and occasionally with gold. Notable Occurrences include many localities throughout the world, but well known from sites in Midwestern quarries of the USA; Ontario, Canada; Switzerland; Pamplona, Spain and in Mexico. Best Field Indicators are typical pink color, crystal habit, hardness, slow reaction to acid, density and luster.

The Borates Subclass

A Subclass of the Carbonate Class of Minerals

The Borate minerals are more complex in their structures than typical carbonates, but because of the scarcity and limited distribution of boron in the Earth's crust there are only a few borates that can be considered common. Because boron in the BO3 ionic group has a positive three (+3) charge, it only requires half of the bond strength of each negative two (-2) oxygen. This allows the oxygens to bond with other borons evenly and thus link boron groups together into compound groups, chains, sheets and even a framework structure using BO4 tetrahedrons linked to BO3 groups. This makes the borates similar to the many structural variations found in the Silicate Class of minerals. These structural variations explain the large size of this subclass in terms of numbers of species. The chemistry is certainly not the culprit. There is little variation in the chemistry of these minerals as a quick scan of the list below reveals mostly sodium, calcium and/or magnesium borates, many with hydroxides, many hydrated and some with chlorine; but little else in terms of chemical variation.

THE MINERAL BORACITE

Chemistry: Mg3B7O13Cl, Magnesium Borate Chloride. Class: Carbonates Subclass: Borates Uses: An ore of boron for boric acid and borax (a cleaning agent and useful industrial chemical) and as mineral specimens. Specimens

Boracite is an interesting borate mineral. It has good color, clarity and hardness to be a gemstone and yet it is rarely cut for this purpose. Probably because it is slightly soluble in water and ordinary wear dulls its surface. It is an attractive mineral for mineral specimens though. Boracite is similar to quartz, in that it has high temperature and low temperature phases. The high temperature phase is cubic and forms nice well shaped cubes and octahedrons that are often modified by other isometric forms. The low temperature orthorhombic phase is the only phase that is stable at normal surface temperatures. This means that when the high temperature phase cools down, it converts to the low temperature phase. The conversion is easily accomplished and does not alter the outward appearance of the crystal, preserving the isometric forms. Therefore the specimens of boracite in a collection are actually the orthorhombic phase in the isometric crystal forms. Mineralogists refer to this as a pseudomorph, or "false shape". Boracite is an evaporite mineral and is not surprisingly found with other evaporite minerals like anhydrite, gypsum and halite. Its crystals are often embedded in these other evaporite minerals suggesting that they formed later than the others, especially since the crystals are in the high temperature phase.

A variety of boracite is called "strassfurtite" and is a fibrous form found at Strassfurt, Germany.

PHYSICAL CHARACTERISTICS:

Color is white to colorless and with pale tints of yellow, green and blue. Luster is vitreous. Transparency: Crystals are transparent to translucent. Crystal System is orthorhombic; 2/m 2/m 2/m , isometric; 4/m bar 3 2/m at high temperatures. Crystal Habits include highly modified cubes and octahedrons which are actually pseudomorphs of the high temperature isometric phase. Also massive, fibrous, nodular and as embedded grains. Cleavage is absent. Fracture is uneven or conchoidal. Hardness is 7 - 7.5 Specific Gravity is approximately 2.9 - 3.0 (average for translucent minerals) Streak is white. Other Characteristics: Slightly soluble in water. Associated Minerals are anhydrite, gypsum, halite and other evaporite minerals. Notable Occurrences include Yorkshire, England; Strassfurt, Germany; Bolivia; Chactaw Salt Dome, Louisiana and Otis, California, USA and France. Best Field Indicators are crystal habit, color, associations, locality, lack of cleavage and the high hardness.

THE MINERAL NITRATINE OR SODA NITER

Chemistry: NaNO3, Sodium Nitrate Class: Carbonates Subclass: Nitrates Uses: as a source of nitrate for fertilizer and as mineral specimens. Specimens

Nitratine or soda niter is one of the few nitrate minerals that is available on the mineral markets. Nitrates are not all that commonly found due to their general ease in dissolving in water. In fact some solid nitrate crystals will even become liquid by removing water from the moisture in the air, a process called deliquescence. Nitratine is deliquescent and is very soluble in water and thus care should be taken to preserve valuable specimens in air tight containers with desiccant. Most nitrates are found in arid,

desert regions such as around the Persian Gulf or found as efflorescences on dry cave or mine walls. Nitrates are similar to carbonates. The nitrogen is surrounded by three oxygens and forms a tight flat triangular NO3 ion group just like the carbonate triangular CO3 ion group. Thus nitrates are placed in the Carbonate Class of minerals. But there are some differences. The nitrogen has a higher charge (+5) and is smaller than the carbon (+4) and thus the nitrogen holds the oxygens a lot closer and the nitrogen oxygen bonds are stronger. Also the overall charge of the nitrate ion group is only negative one (-1) compared to the carbonate's ion group's charge of negative two (-2). These differences show up in a greater difficulty in breaking apart the nitrate ion group as is usually an easy task for acids with the carbonate ion group, greater solubility and a much less diverse subclass of minerals. Nitratine is most similar to the trigonal carbonates or those carbonates that belong to the Calcite Group, specifically magnesite, rhodochrosite, siderite, smithsonite, sphaerocobaltite and of course calcite and some rarer members. The structures of nitratine and the members of the Calcite Group are analogous and they therefore share many similar properties such as symmetry and crystal habits. The structures are so similar that nitratine in a laboratory can grow onto a crystal of calcite and essentially finish the crystal with nitratine instead calcite. Another nitrate called niter, KNO3 (also known as "saltpeter") is more similar to the Aragonite Group of carbonate minerals. Nitratine is similar to its rarer cousin niter but is deliquescent and gives a different result in a flame test. The flame test is where a sample is burned in a flame and gives off a certain color. For niter the flame should be violet, an indicator of potassium, and for nitratine the flame should be yellow, an indicator of sodium. Nitratine was an important source of nitrates for fertilizer and other chemical uses including fireworks. Nowadays, fixed nitrogen from the air has all but replaced nitratine as the main source of nitrogen. An interesting side note is that discarded specimens of nitratine were said to have been thrown into a garden and this is how the importance of nitrates in good plant growth was first discovered.

PHYSICAL CHARACTERISTICS:

Color is white or gray, sometimes with tints of red-brown or yellow. Luster is vitreous. Transparency crystals are translucent to transparent. Crystal System is trigonal; bar 3 2/m Crystal Habits include masses and soil deposits in arid and desert regions. Crystals are rare, but when found are in the form of rhombohedrons similar to calcite's crystals. Cleavage is perfect in three directions forming rhombohedrons.

Fracture is conchoidal. Hardness is 1.5 - 2. Specific Gravity is approximately 2.2 - 2.3 (below average) Streak is white. Associated Minerals gypsum, halite and other arid region minerals. Other Characteristics: Deliquescent, slightly sectile, very soluble in water and gives a yellow flame test result. Notable Occurrences include the Tarapaca and other northern Chile sites; Bolivia; Peru and Humboldt Co., Nevada, San Bernardino Co., California and New Mexico, USA. Best Field Indicators are crystal habit, flame test, solubility, deliquescence, hardness, occurrence and cleavage.