Bituminous

Bitumen ( , ) is an immensely viscous constituent of petroleum. Depending on its exact composition, it can be a sticky, black liquid or an apparently solid mass that behaves as a liquid over very large time scales. In American English, the material is commonly referred to as asphalt or tar. Whether found in natural deposits or refined from petroleum, the substance is classed as a pitch. Prior to the 20th century, the term asphaltum was in general use. The word derives from the Ancient Greek word (), which referred to natural bitumen or pitch. The largest natural deposit of bitumen in the world is the Pitch Lake of southwest Trinidad, which is estimated to contain 10 million tons.

About 70% of annual bitumen production is destined for road construction, its primary use. In this application, bitumen is used to bind aggregate particles like gravel and forms a substance referred to as asphalt concrete, which is colloquially termed ''asphalt''. Its other main uses lie in bituminous waterproofing products, such as roofing felt and roof sealant.

In material sciences and engineering, the terms ''asphalt'' and ''bitumen'' are often used interchangeably and refer both to natural and manufactured forms of the substance, although there is regional variation as to which term is most common. Worldwide, geologists tend to favor the term ''bitumen'' for the naturally occurring material. For the manufactured material, which is a refined residue from the distillation process of selected crude oils, ''bitumen'' is the prevalent term in much of the world; however, in American English, ''asphalt'' is more commonly used. To help avoid confusion, the terms "liquid asphalt", "asphalt binder", or "asphalt cement" are used in the U.S. to distinguish it from asphalt concrete. Colloquially, various forms of bitumen are sometimes referred to as " tar", as in the name of the La Brea Tar Pits.

Naturally occurring bitumen is sometimes specified by the term ''crude bitumen''. Its viscosity is similar to that of cold molasses while the material obtained from the fractional distillation of crude oil boiling at is sometimes referred to as "refined bitumen". The Canadian province of Alberta has most of the world's reserves of natural bitumen in the Athabasca oil sands, which cover , an area larger than England.

Terminology

Etymology

The Latin word traces to the Proto-Indo-European root '' *gʷet-'' "pitch".

The word "asphalt" is derived from the late Middle English, in turn from French ''asphalte'', based on Late Latin ''asphaltum'', which is the latinisation of the Greek (''ásphaltos''), a word meaning "asphalt/bitumen/ pitch", which perhaps derives from , "not, without", i.e. the alpha privative, and (''sphallein''), "to cause to fall, baffle, (in passive) err, (in passive) be balked of".

The first use of asphalt by the ancients was as a cement to secure or join various objects, and it thus seems likely that the name itself was expressive of this application. Specifically, Herodotus mentioned that bitumen was brought to Babylon to build its gigantic fortification wall.

From the Greek, the word passed into late Latin, and thence into French (''asphalte'') and English ("asphaltum" and "asphalt"). In French, the term ''asphalte'' is used for naturally occurring asphalt-soaked limestone deposits, and for specialised manufactured products with fewer voids or greater bitumen content than the "asphaltic concrete" used to pave roads.

Modern terminology

Bitumen mixed with clay was usually called "asphaltum", but the term is less commonly used today.

In American English, "asphalt" is equivalent to the British "bitumen". However, "asphalt" is also commonly used as a shortened form of "asphalt concrete" (therefore equivalent to the British "asphalt" or " tarmac").

In Canadian English, the word "bitumen" is used to refer to the vast Canadian deposits of extremely heavy crude oil, while "asphalt" is used for the oil refinery product. Diluted bitumen (diluted with naphtha to make it flow in pipelines) is known as " dilbit" in the Canadian petroleum industry, while bitumen " upgraded" to synthetic crude oil is known as "syncrude", and syncrude blended with bitumen is called "synbit".

"Bitumen" is still the preferred geological term for naturally occurring deposits of the solid or semi-solid form of petroleum. "Bituminous rock" is a form of sandstone impregnated with bitumen. The oil sands of Alberta, Canada are a similar material.

Neither of the terms "asphalt" or "bitumen" should be confused with tar or coal tars. Tar is the thick liquid product of the dry distillation and pyrolysis of organic hydrocarbons primarily sourced from vegetation masses, whether fossilized as with coal, or freshly harvested. The majority of bitumen, on the other hand, was formed naturally when vast quantities of organic animal materials were deposited by water and buried hundreds of metres deep at the diagenetic point, where the disorganized fatty hydrocarbon molecules joined in long chains in the absence of oxygen. Bitumen occurs as a solid or highly viscous liquid. It may even be mixed in with coal deposits. Bitumen, and coal using the Bergius process, can be refined into petrols such as gasoline, and bitumen may be distilled into tar, not the other way around.

Composition

Normal composition

The components of bitumen include four main classes of compounds:
* Naphthene aromatics (naphthalene), consisting of partially hydrogenated polycyclic aromatic compounds
* Polar aromatics, consisting of high molecular weight phenols and carboxylic acids produced by partial oxidation of the material
* Saturated hydrocarbons; the percentage of saturated compounds in asphalt correlates with its softening point
* Asphaltenes, consisting of high molecular weight phenols and heterocyclic compounds

Bitumen typically contains, elementally 80% by weight of carbon; 10% hydrogen; up to 6% sulfur; and molecularly, between 5 and 25% by weight of asphaltenes dispersed in 90% to 65% maltenes. Most natural bitumens also contain organosulfur compounds, nickel and vanadium are found at <10 parts per million, as is typical of some petroleum. The substance is soluble in carbon disulfide. It is commonly modelled as a colloid, with asphaltenes as the dispersed phase and maltenes as the continuous phase. "It is almost impossible to separate and identify all the different molecules of bitumen, because the number of molecules with different chemical structure is extremely large".

Asphalt may be confused with coal tar, which is a visually similar black, thermoplastic material produced by the destructive distillation of coal. During the early and mid-20th century, when town gas was produced, coal tar was a readily available byproduct and extensively used as the binder for road aggregates. The addition of coal tar to macadam roads led to the word " tarmac", which is now used in common parlance to refer to road-making materials. However, since the 1970s, when natural gas succeeded town gas, bitumen has completely overtaken the use of coal tar in these applications. Other examples of this confusion include La Brea Tar Pits and the Canadian tar sands, both of which actually contain natural bitumen rather than tar. "Pitch" is another term sometimes informally used at times to refer to asphalt, as in Pitch Lake.

Additives, mixtures and contaminants

For economic and other reasons, bitumen is sometimes sold combined with other materials, often without being labeled as anything other than simply "bitumen".Arnold, Terence S. (senior research chemist, Pavement Materials Team, Office of Infrastructure Research and Development, Federal Highway Administration; Federal lab manager for the chemistry lab, Turner-Fairbank Highway Research Center; fellow of the Royal Society of Chemistry in the United Kingdom)
"What's in Your Asphalt?,"
September 2017 (last modified 25 October 2017), ''Public Roads'', FHWA-HRT-17-006.htm," Office of Research, Development, and Technology, Office of Corporate Research, Technology, and Innovation Management, Federal Highway Administration, U.S. Department of Transportation

Of particular note is the use of re-refined engine oil bottoms – "REOB" or "REOBs"the residue of recycled automotive engine oil collected from the bottoms of re-refining vacuum distillation towers, in the manufacture of asphalt. REOB contains various elements and compounds found in recycled engine oil: additives to the original oil and materials accumulating from its circulation in the engine (typically iron and copper). Some research has indicated a correlation between this adulteration of bitumen and poorer-performing pavement.

Occurrence

The majority of bitumen used commercially is obtained from petroleum. Nonetheless, large amounts of bitumen occur in concentrated form in nature. Naturally occurring deposits of bitumen are formed from the remains of ancient, microscopic algae (diatoms) and other once-living things. These natural deposits of bitumen have been formed during the Carboniferous period, when giant swamp forests dominated many parts of the Earth. They were deposited in the mud on the bottom of the ocean or lake where the organisms lived. Under the heat (above 50°C) and pressure of burial deep in the earth, the remains were transformed into materials such as bitumen, kerogen, or petroleum.

Natural deposits of bitumen include lakes such as the Pitch Lake in Trinidad and Tobago and Lake Bermudez in Venezuela. Natural seeps occur in the La Brea Tar Pits and the McKittrick Tar Pits in California, as well as in the Dead Sea.

Bitumen also occurs in unconsolidated sandstones known as "oil sands" in Alberta, Canada, and the similar "tar sands" in Utah, US.
The Canadian province of Alberta has most of the world's reserves, in three huge deposits covering , an area larger than England or New York state. These bituminous sands contain of commercially established oil reserves, giving Canada the third largest oil reserves in the world. Although historically it was used without refining to pave roads, nearly all of the output is now used as raw material for oil refineries in Canada and the United States.

The world's largest deposit of natural bitumen, known as the Athabasca oil sands, is located in the McMurray Formation of Northern Alberta. This formation is from the early Cretaceous, and is composed of numerous lenses of oil-bearing sand with up to 20% oil. Isotopic studies show the oil deposits to be about 110 million years old. Two smaller but still very large formations occur in the Peace River oil sands and the Cold Lake oil sands, to the west and southeast of the Athabasca oil sands, respectively. Of the Alberta deposits, only parts of the Athabasca oil sands are shallow enough to be suitable for surface mining. The other 80% has to be produced by oil wells using enhanced oil recovery techniques like steam-assisted gravity drainage.

Much smaller heavy oil or bitumen deposits also occur in the Uinta Basin in Utah, US. The Tar Sand Triangle deposit, for example, is roughly 6% bitumen.

Bitumen may occur in hydrothermal veins. An example of this is within the Uinta Basin of Utah, in the US, where there is a swarm of laterally and vertically extensive veins composed of a solid hydrocarbon termed Gilsonite. These veins formed by the polymerization and solidification of hydrocarbons that were mobilized from the deeper oil shales of the Green River Formation during burial and diagenesis.

Bitumen is similar to the organic matter in carbonaceous meteorites. However, detailed studies have shown these materials to be distinct. The vast Alberta bitumen resources are considered to have started out as living material from marine plants and animals, mainly algae, that died millions of years ago when an ancient ocean covered Alberta. They were covered by mud, buried deeply over time, and gently cooked into oil by geothermal heat at a temperature of . Due to pressure from the rising of the Rocky Mountains in southwestern Alberta, 80 to 55 million years ago, the oil was driven northeast hundreds of kilometres and trapped into underground sand deposits left behind by ancient river beds and ocean beaches, thus forming the oil sands.

History

Paleolithic times

Bitumen use goes back to the Middle Paleolithic, where it was shaped into tool handles or used as an adhesive for attaching stone tools to hafts.

The earliest evidence of bitumen use was discovered when archeologists identified bitumen material on Levallois flint artefacts that date to about 71,000 years BP at the Umm el Tlel open-air site, located on the northern slope of the Qdeir Plateau in el Kowm Basin in Central Syria. Microscopic analyses found bituminous residue on two-thirds of the stone artefacts, suggesting that bitumen was an important and frequently-used component of tool making for people in that region at that time. Geochemical analyses of the asphaltic residues places its source to localized natural bitumen outcroppings in the Bichri Massif, about 40 km northeast of the Umm el Tlel archeological site.

A re-examination of artifacts uncovered in 1908 at Le Moustier rock shelters in France has identified Mousterian stone tools that were attached to grips made of ochre and bitumen. The grips were formulated with 55% ground goethite ochre and 45% cooked liquid bitumen to create a moldable putty that hardened into handles. Earlier, less-careful excavations at Le Moustier prevent conclusive identification of the archaeological culture and age, but the European Mousterian style of these tools suggests they are associated with Neanderthals during the late Middle Paleolithic into the early Upper Paleolithic between 60,000 and 35,000 years before present. It is the earliest evidence of multicomponent adhesive in Europe.

Ancient times

The use of natural bitumen for waterproofing and as an adhesive dates at least to the fifth millennium BC, with a crop storage basket discovered in Mehrgarh, of the Indus Valley civilization, lined with it. By the 3rd millennium BC refined rock asphalt was in use in the region, and was used to waterproof the Great Bath in Mohenjo-daro.

In the ancient Near East, the Sumerians used natural bitumen deposits for mortar between bricks and stones, to cement parts of carvings, such as eyes, into place, for ship caulking, and for waterproofing. The Greek historian Herodotus said hot bitumen was used as mortar in the walls of Babylon.

The long Euphrates Tunnel beneath the river Euphrates at Babylon in the time of Queen Semiramis () was reportedly constructed of burnt bricks covered with bitumen as a waterproofing agent.

Bitumen was used by ancient Egyptians to embalm mummies. The Persian word for asphalt is ''moom'', which is related to the English word mummy. The Egyptians' primary source of bitumen was the Dead Sea, which the Romans knew as ''Palus Asphaltites'' (Asphalt Lake).

In approximately 40 AD, Dioscorides described the Dead Sea material as ''Judaicum bitumen'', and noted other places in the region where it could be found. The Sidon bitumen is thought to refer to material found at Hasbeya in Lebanon. Pliny also refers to bitumen being found in Epirus. Bitumen was a valuable strategic resource. It was the object of the first known battle for a hydrocarbon deposit – between the Seleucids and the Nabateans in 312 BC.

In the ancient Far East, natural bitumen was slowly boiled to get rid of the higher fractions, leaving a thermoplastic material of higher molecular weight that, when layered on objects, became hard upon cooling. This was used to cover objects that needed waterproofing, such as scabbards and other items. Statuettes of household deities were also cast with this type of material in Japan, and probably also in China.

In North America, archaeological recovery has indicated that bitumen was sometimes used to adhere stone projectile points to wooden shafts. In Canada, aboriginal people used bitumen seeping out of the banks of the Athabasca and other rivers to waterproof birch bark canoes, and also heated it in smudge pots to ward off mosquitoes in the summer. Bitumen was also used to waterproof plank canoes used by indigenous peoples in pre-colonial southern California.

Continental Europe

In 1553, Pierre Belon described in his work '' Observations'' that ''pissasphalto'', a mixture of pitch and bitumen, was used in the Republic of Ragusa (now Dubrovnik, Croatia) for tarring of ships.

An 1838 edition of ''Mechanics Magazine'' cites an early use of asphalt in France. A pamphlet dated 1621, by "a certain Monsieur d'Eyrinys, states that he had discovered the existence (of asphaltum) in large quantities in the vicinity of Neufchatel", and that he proposed to use it in a variety of ways – "principally in the construction of air-proof granaries, and in protecting, by means of the arches, the water-courses in the city of Paris from the intrusion of dirt and filth", which at that time made the water unusable. "He expatiates also on the excellence of this material for forming level and durable terraces" in palaces, "the notion of forming such terraces in the streets not one likely to cross the brain of a Parisian of that generation".

But the substance was generally neglected in France until the revolution of 1830. In the 1830s there was a surge of interest, and asphalt became widely used "for pavements, flat roofs, and the lining of cisterns, and in England, some use of it had been made of it for similar purposes". Its rise in Europe was "a sudden phenomenon", after natural deposits were found "in France at Osbann (Bas-Rhin), the Parc ( Ain) and the Puy-de-la-Poix (Puy-de-Dôme

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