ALL ABOUT LIME

by Terry Montlick 10/4/11

Revised 10/14/11 The term lime is used for a host of different calcium-containing chemical compounds. There are oxides and hydroxides of calcium, silicon, magnesium, aluminum, and iron. Some are good for growing mushrooms and some are not. Any mushroom instructions which just specify lime are nearly useless. You need to know which kind of lime. The following is rundown of the usual suspects.

Sulfates
CALCIUM SULPHATE DIHYDRATE CaSO42H2O
Gypsum = garden lime = mineral white = terra alba = light spar = precipitated calcium = calcium sulfate dihydrate, CaSO42H2O. This is a grayish powder. To make things extra confusing, the dihydrate form of calcium sulfate (calcium sulfate dihydrate, CaSO42H2O), is frequently referred to as simply calcium sulfate. Technically, the term calcium sulfate refers to the anhydrous form, with the formula CaSO4. Fortunately, the two chemicals have virtually the same solubility in water. Almost the same amounts of calcium and sodium will go into solution. This means that for mushroom cultivation, they can pretty much be used interchangeably. Calcium sulfate dehydrate acts as a pH buffer, maintaining a neutral pH. Mycological use: Spawn making. It prevents the clumping of the grain kernels and acts as a pH buffer. It can also be added to wood and manure-based substrates at the rate of 3-5% of the dry weight to improve structure and porosity. It has been found to stimulate mycelial growth in wood-based shiitake substrate, as well as improve fruitbody formation and development. It may also be used in combination with calcium carbonate for a casing layer. Calcium carbonate offsets the acidity of peat moss, while calcium sulfate dihydrate provides particle looseness (particle separation) and mineral salts, especially sulfur and calcium. RR points out that the calcium sulfate, being slow to dissolve, provides long term buffering of the casing. Stamets recommends it be used in the ratios (by volume) of 0.5 units of calcium sulfate dihydrate, 0.5 units of calcium carbonate, to 10 units of peat moss.

Heating calcium sulfate dihydrate to between 100C to 125C (212F to 257F) for a few hours partially dehydrates the mineral, driving off approximately 75% of the water contained in its chemical structure: CaSO42H2O + heat CaSO4H2O + 1H2O (steam) This creates another kind of lime, CALCIUM SULFATE HEMIHYDRATE.

CALCIUM SULFATE HEMIHYDRATE CaSO4nH2O

Plaster of Paris = calcined gypsum = dried gypsum = calcium sulfate hemihydrate, CaSO4nH2O, where n is in the range 0.5 to 0.8. When calcined gypsum is mixed with water at normal temperatures, it quickly reverts the preferred dihydrate form. It physically "sets" to form a rigid and relatively strong gypsum crystal lattice: CaSOH2O + 1 H2O CaSO42H2O + heat and we are back to CALCIUM SULFATE DIHYDRATE. Another thing that can be done with calcium sulfate dihydrate (CaSO42H2O, gypsum) is remove all the H2O rather than just some of it, as is done to make calcium sulfate hemihydrate. It is first heated to the range 116-121C (241F-250F). Its boiled at this temperature until its water content is reduced from 20.9% down to 5%-6%. It is then heated to 206 C (402 F). At this point, virtually all the water has been driven off. Overall, we have: CaSO42H2O + heat CaSO4 + 2H20 This reaction produces CALCIUM SULFATE. Mycological use: None, unless you first mix it with water to make calcium sulfate dehydrate, which you will then have to pulverize. If you use it directly, your spawn will solidify into a solid mass held together by plaster of Paris!

CALCIUM SULFATE CaSO4

Anhydrous calcium = sometimes garden lime (mixed with mostly gypsum) = sidewalk chalk = Drierite = calcium sulfate = CaSO4. This is a white powder. In addition to being made from calcium sulfate dihydrate (CaSO42H2O , gypsum), it can be extracted directly from mines and quarries. It is found in evaporite deposits with gypsum, and is commonly used as a desiccant. Calcium sulfate acts as a pH buffer, maintaining a neutral pH. Its solubility is about the same as calcium sulfate dihydrate (CaSO42H2O), which is 2 grams per liter of water.

Even though calcium sulfate and calcium sulfate dihydrate have around the same solubility, calcium sulfate contains 26.5% more calcium sulfate than calcium sulfate dihydrate. This is because part of the weight of calcium sulfate dihydrate is made up of bound water. For purposes of mycology, it is almost interchangeable with calcium sulfate dihydrate, CaSO42H2O. Calcium sulfate, however, is 26.5% more concentrated. Mycological use: Spawn making. It prevents the clumping of the grain kernels and acts as a pH buffer. It can also be added to wood and manure-based substrates at the rate of 3-5% of the dry weight to improve structure and porosity. It has been found to stimulate mycelial growth in wood-based shiitake substrate, as well as improve fruitbody formation and development.

Carbonates
CALCIUM CARBONATE CaCO3
Limestone = limestone flour = limestone grit (when particles are coarse) = true chalk = ground oyster shells = ground egg shells = mineral calcite = calcium carbonate, CaCO3. It is a white powder. Calcium carbonate is insoluble in water, and would be of little use for influencing pH except for a chemical reaction: CaCO3 + CO2 + H2O Ca(HCO3)2 This says that calcium carbonate plus water which has carbon dioxide dissolved in it will produce calcium bicarbonate (Ca(HCO3)2). Actually, there is an intermediate reaction of carbon dioxide with water which generates carbonic acid (H2CO3): CO2 + H2O H2CO3 The carbonic acid reacts with calcium carbonate to form calcium bicarbonate: H2CO3 + CaCO3 Ca(HCO3)2 Note that not all of the left sides of these equations will fully transform to the right sides. The , rather than indicates that there is an equilibrium between the two sides of the equations.

Calcium bicarbonate is not only soluble in water, but it has a lot of pH buffering capacity. At a temperature of 25 C and atmospheric levels of ambient carbon dioxide, calcium carbonate saturating a water solution has a pH of 8.3, and so is somewhat alkaline. This rate of calcium bicarbonate is 47 mg/liter. Mycological use: Buffers the pH of a casing. It counteracts the acidity of peat and other casing materials. It may also be used in combination with calcium sulfate dihydrate for a casing layer. Calcium carbonate offsets the acidity of peat moss, while calcium sulfate dihydrate provides particle looseness (particle separation) and mineral salts, especially sulfur and calcium. RR points out that the calcium sulfate, being slow to dissolve, provides long term buffering of the casing. Stamets recommends it be used in the ratios (by volume) of 0.5 units of calcium sulfate dihydrate and 0.5 units of calcium carbonate to 10 units of peat moss. Calcium carbonate can be heated to produce calcium oxide (most commonly referred to as quicklime). Commercially, this is done by feeding quarried limestone through crusher, which reduces it to small bits. These are put into a hot lime kiln, and the temperature is raised to over 441 C (825 F), a process called calcination or lime-burning. This liberates a molecule of carbon dioxide (CO2): CaCO3 + heat CaO + CO2 This produces CALCIUM OXIDE.

CALCIUM OXIDE CaO

Quicklime = burnt lime = unslaked lime = calcium oxide, CaO. It is a white, caustic, alkaline crystalline solid at room temperature. Most of the time, the word lime refers to calcium oxide, but by no means always. Calcium oxide is not stable and, when cooled, will spontaneously react with CO2 from the air until, after enough time, it is transforms according to this process: CaO + CO2 CaCO3 + heat Which gets us back to CALCIUM CARBONATE.. This is not the only chemical reaction possible. Calcium oxide reacts violently with water, producing so much heat that ignition of combustibles and severe burns may result! CaO + H2O Ca(OH)2 + heat This is CALCIUM HYDROXIDE. 4

Mycological use: None. Do not mix with water!

CALCIUM HYDROXIDE Ca(OH)2)

Hydrated lime = horticultural lime = builders lime = slaked lime = cal = pickling lime = calcium hydroxide, Ca(OH)2. It is a white powder. Mycological use: It is extremely alkaline and water soluble. Used in a water bath for straw, competitor fungi and bacteria are rendered inactive. In GGMM, Stamets recommends dissolving it in the amount of 0.5-1% by weight of water. This concentration is equivalent to 2-4 pounds of calcium hydroxide to 50 gallons of water. However, Mycelio points out that a fully saturated solution of calcium hydroxide is only 0.17% by weight. This means that a maximum of 11.3 ounces will dissolve in 50 gallons of water. This information has been verified from multiple sources. Stamets further says that his amount of calcium hydroxide will increase the pH to 9.5 or higher. But Mycelio states that a fully saturate solution has a pH above 12.1. This has also been verified in the literature. Mycellio usually finds pH values like 12.3 and 12.4. When heated to 512 C, the partial pressure of water in equilibrium with calcium hydroxide reaches 101 kPa. This decomposes the calcium hydroxide into calcium oxide and water: Ca(OH)2 + heat CaO + H2O This gets us back to CALCIUM OXIDE. There is one more calcium compound called lime. This is CALCIUM MAGNESIUM CARBONATE.

CALCIUM MAGNESIUM CARBONATE CaMg(CO3)2

Dolomite = a component, in varying amounts along with calcium carbonate, of dolomitic limestone or dolomitic hydrated lime = calcium magnesium carbonate, (CaMg)(CO3)2. It is normally obtained by mining the mineral magnesite. Dolomite is sold as garden lime, and pellets of it can be found in feed stores as a mineral supplement for goats and other livestock. Mycological use: Buffers the pH of casing material. Caution: if used in too high a concentration, the magnesium content can depress mycelial growth or have a negative effect on fruiting performance.