Bitumen (Petrochemical Product)

Eight black residues, scraped from outer surfaces of painted ceramics, unearthed from graves 1–3 at Başur Höyük (SE Turkey), were analysed by geochemical techniques in order to characterize bitumens and to try to identify their source. Ceramics are dated from the Early Bronze period (3100–2900 BCE). The black organic matter was indeed identified as bitumen, but its source has not been discovered despite its comparison with several oil seeps from the area. The bitumen at Başur Höyük does not match the bitu-mens analyzed at Kavuşan Höyük, Salat Höyük, Hakemi Use and Kuriki Höyük which are Cretaceous in origin and likely imported from the Eruh tars deposit. The stable carbon isotope values of their asphaltene fraction suggest a Silurian origin, however the occurrence of the 18a(H)-oleanane emphasized a younger source, i.e. Tertiary or Cretaceous. Our interpretation favours the mixture of two oils, a Silurian age and a Tertiary-Cretaceous age. This mixture may occur geologically, due to the uptake of a Tertiary signal by a Silurian oil along its migration route to the surface. It may also be a consequence of human activity carried out by the inhabitants at the mortuary ceremony where the bituminous mixture has been applied to ceramics, prior to their deposit in the graves. The oil seep character of the archaeological bitumen at Başur Höyük and the lack of obvious oxidation suggest the following explanation: freshly collected oil seeps were splashed on ceramics as ritual practices and the tarry potteries were then buried and therefore sealed. The fast burial prevented the bitumen from any oxidative alteration.

ABSTRACT The primary objective of this full-scale accelerated pavement testing was to evaluate the performance of unmodified and polymer modified asphalt binders and to recommend improved specification tests over existing SUperior PERforming Asphalt PAVEment (Superpave®) binder performance grading methodologies.

Asphaltum, often referred to as bitumen, is a naturally occurring form of petroleum that was used by
ancient cultures for thousands of years. Asphaltum deposits are found throughout the world and occur
both on land and submerged under water. Ethnohistoric accounts of native Californians suggest that
asphaltum from terrestrial seeps was shaped by hand into cakes and traded throughout Southern California
and was the only grade of asphaltum used to manufacture plank-canoes. While there are no
terrestrial seeps on the California Channel Islands, drift asphaltum exuded from submarine seeps can
frequently be found washed up on the shore. It remains unclear to what extent prehistoric island
populations relied on this drift asphaltum and whether or not they acquired terrestrial asphaltum
through trade. This study combines gas chromatography/mass spectrometry (GC/MS) and liquid chromatography
coupled with carbon isotopic analysis in an effort to identify the sources of six archaeological
bituminous mixtures from San Nicolas and San Miguel islands. We compare the archaeological
asphaltum to four modern samples collected from marine tarballs and a mainland terrestrial seep.
Further, we compare our results to a USGS chemometric database to determine if our archaeological
samples match extant sources. Our results show that prehistoric peoples on the Channel Islands utilized
drift asphaltum from submarine seeps in a variety of technological applications throughout the Holocene.
The methods used in our study are globally applicable and can be used to address a variety of broad
anthropological questions.

En 2012 se inició un programa de estudio químico mediante extracción de residuos de aglutinantes en 14 muestras de rellenos, adobes, pisos y aplanados, fechadas de 200-400 d.C., obtenidos en excavaciones en edificios de arquitectura de tierra monumental del sitio arqueológico de La Joya, Veracruz, México, ubicado en la planicie costera del Golfo en un ambiente de trópico húmedo. El interés por identificar un aglutinante orgánico deriva de la observación que la conservación de los edificios es mejor que la esperada considerando solo la composición mineral de los materiales de construcción, donde dominan arcillas expansivas de tipo montmorillonita, lo que lleva a suponer la presencia de un componente con efectos consolidantes e hidrofugantes.
El estudio químico de las muestras consistió en la extracción de residuos orgánicos mediante solventes hexano y metanol, y su análisis por medio de cromatografía de capa fina, espectroscopía de IR, Resonancia Magnética Nuclear protónica y de carbono 13, y espectrometría de masas. Los resultados hasta la fecha muestran la presencia de una mezcla de compuestos similar en todas las muestras, con mayor cantidad en los adobes. Los componentes identificados a la fecha consisten en hidrocarburos, un triglicérido y un azúcar. Para la identificación del origen del aglutinante, se están realizando de manera paralela estudios químicos de mucílagos usados en arquitectura vernácula en Centroamérica.
La importancia de identificar el aglutinante presente en la arquitectura prehispánica no solo reside en entender lo que hizo posible por miles de años una tradición constructiva de tierra cruda en un ambiente de trópico húmedo, tópico que releva de la historia de la tecnología, sino por las posibilidades que abre en la conservación de los vestigios arqueológicos y su posible aplicación a la construcción moderna.

In the wake of a growing bitumen binder variability resulting from economic and geopolitical constraints leading to changes in crude oils and refining processes, the asphalt industry is facing challenges of quality, consistency and early pavement failures in the form of cracking and raveling in particular. New, innovative and relevant analytical tools and approaches are being developed particularly at the Western Research Institute (WRI) to address the challenges and advance from trials and errors to modelling and predictions. Studies launched by WRI have demonstrated the proof of concept, and the validation of chemometric correlations; linking chemical composition of bitumen binders to their physical properties and their performance in mixes. Relevant strong correlations were obtained for compositional fractions, chemical functionalities, and thermal parameters with binder rheological properties, specification parameters, as well as asphalt mix properties, through a study with a road contractor. Hence, the binder impacts mixture stiffness and fatigue resistance, but less prominently in mixture resistance to moisture-induced damaged, rutting resistance and compaction properties, where aggregates become more prominent. Other important results confirmed some performance indicators from binder to mixes, such as the stiffness modulus, fatigue parameters, thermal cracking parameters (relaxation and cracking temperature), and rutting resistance. New possible indicators were detected like the binder glass transition and crossover temperatures as well as their difference, named temperature of intermediate region (TIR) with respect to cracking resistance and healing propensity. The effect of long term aging, particularly with respect to cracking, was also evaluated. Many of these results have been obtained through two major projects: the Asphalt Industry Research Consortium launched by WRI which is ongoing on a very wide binder range aiming to chemically fingerprint binders to predict their mechanical properties as well as their aging susceptibility and their compatibility with various modifiers or recycled materials. The second project is the ongoing National Cooperative Highway Research Program 09-60 project. This involves studying the impact of binder resistance to internal restraint damage mechanism on mixture cracking, and the influence of other thermal cracking factors such as, long-term aging and reversible time-dependent physical hardening. The ultimate goal of this project is to develop and propose new and more relevant specification parameters to avoid age-induced surface damage in the form of transverse cracking, block cracking, and raveling.

Well-documented transverse cracking failures require external restraint to impose tensile stresses on the mix, as modeled from the Thermal Stress-Restrained Specimen Test (TSRST). When specimens are restrained, any transverse crack relieves building stresses and lowers the probability for a second crack nearby. But finite element analysis, as well as experimental evidence from acoustic emissions, as well as Sliver (mixture-Bending Beam Rheometer BBR) testing followed by binder extraction with Hirsch modeling, support the conclusion that asphalt concrete can be damaged on cooling even when no external restraint is imposed. This internal restraint damage mechanism is now thought to be the primary cause for surface block cracking and raveling. Moreover, block cracking and raveling are considered age-induced pavement distresses, where aging causes asphalt pavement materials to stiffen and embrittle, which leads to a high cracking potential. The hypothesized "internal restraint" model is predicated on the fact that asphalt mastic contracts significantly more than the surrounding aggregate skeleton, thereby creating thermal stresses within the binder as the mixture cools. FEA modeling of the internal restraint damage mechanism indicates that: (1) Peak stresses occur in the mastic in regions where the aggregate particles are closest together. (2) Stresses appear to be high enough to induce Cohesive / adhesive failure. And finally, oxidative aging and thermo-reversible physical hardening have been found to be critical contributors to the negative evolution in binder rheology that aggravates age-induced surface damage. Analytical techniques such as SAR-AD, FTIR, and DSC are used to explain the evolution in chemical properties that cause observed loss in binder quality as noted on Black Space diagrams, or when considering related parameters such as R-value, Tc, G-R, or TIR.

Este trabajo trata de reconstruir, a partir del estudio de muestras de edificios del sitio arqueológico de La Joya, Veracruz, México, la antigua tecnología de construcción de tierra cruda en trópico húmedo. Se realizó el estudio químico de residuos orgánicos en 16 muestras de materiales constructivos prehispánicos: rellenos (tierra apisonado), adobes, pisos y aplanados, fechadas de 200-450 d.C., obtenidos de excavaciones. Se infiere que utilizaron como aditivo chapopote (bitumen ó betún) disuelto en aceite vegetal, partiendo de la interpretación de los componentes identificados: hidrocarburos, ésteres aromáticos y alifáticos, triglicéridos, esteroides, triterpenos, alcoholes de cadena larga y un azúcar. Asimismo se realizaron experimentos en el sitio con los extractos vegetales que se usan actualmente para construcción en tierra en Centroamérica y con bitumen, para comparar su efectividad. La importancia de identificar el aglutinante presente en la arquitectura prehispánica no solo reside en entender lo que hizo posible por miles de años una tradición constructiva de tierra cruda en la zona de trópico húmedo de la planicie costera del Golfo sur de México, del que La Joya es un ejemplo, sino también abre las posibilidades de aplicar la tecnología a la conservación de los vestigios arqueológicos e incluso a la construcción moderna.

Our research aims to reconstruct the ancient technology of raw earthen architecture in a humid tropical environment by chemical analysis of organic residues from 16 samples of pre-Columbian construction material. Various samples of fills (rammed earth), adobes, floors and renders, dated between A.D. 200 and 450, were obtained during the excavations of monumental earthen buildings at the archaeological site of La Joya, Veracruz, México, located on the coastal plain of the Golf of Mexico. We infer that bitumen (chapopote), diluted in vegetable oil, was used to make the earthen construction resistant to rain and wind, according to the interpretation of the chemical components identified: hydrocarbons, aromatic and aliphatic esters, triglycerides, steroids, triterpens, long-chain alcohols and a sugar. For comparative purposes, plant derived additives used in modern day construction in Central America and bitumen were field tested to verify their efficiency. The importance of identifying additives in pre-Colombian earthen architecture resides not only in understanding what made viable an earthen architectural tradition in humid tropical areas for thousand of years, but also provides the possibility to apply the technology to the conservation of archaeological remains and to modern construction.

Com este trabalho pretende-se reconstruir a tecnologia antiga da construção em terra crua num ambiente tropical úmido, através da análise química de resíduos orgânicos de 16 amostras de materiais de construção pré-hispânicos. As amostras de tapia, de adobes, de revestimentos de pavimentos e de rebocos, datadas entre 200 e 450 d.C., foram recolhidas nas escavações da construção monumental de terra do sítio arqueológico de La Joya, Veracruz, México, localizado na planície costeira do Golfo do México. Supõe-se que o betume (chapopote), dissolvido em azeite vegetal, foi utilizado para proteger a construção de terra da chuva e do vento, partindo da interpretação dos componentes mais importantes identificados: hidrocarbonetos, ésteres aromáticos e alifáticos, esteroides, triglicéridos, triterpenos, álcoois de cadeia longa e um açúcar. Para estudos comparativos foram efetuadas e analisadas aplicações in situ com extratos vegetais, que se usam hoje em dia na construção na América central, e betume. A importância da identificação de aditivos e adjuvantes presentes na arquitetura pré-hispânica não reside unicamente na compreensão do que torna viável uma tradição arquitetónica de milhares de anos, à base de terra, numa zona tropical húmida, mas abre também a possibilidadede aplicar essa tecnologia à conservação do patrimônio arqueológico e à construção moderna.

The most common sources of waste products are from the growth of various industries and increase in population. The type of waste which is most hazardous to the nature is the Plastic Waste. The main concern about the plastic waste is its non-biodegradability. According to recent researches plastic waste when mixed with bitumen gives it desired mechanical properties. Bitumen is primarily used in the construction of flexible pavements and when it is mixed with plastic waste it improves the water resistivity, capacity and stability of the mix. Laboratory test have proved that it can be used as a binder material in the bitumen mix for construction of flexible pavements. Plastic waste percentage in bitumen has to be checked. Marshal stability test is the most commonly used method to relate with field conditions. The samples used are made up with bitumen concrete commonly called Asphalt in which plastic content and bitumen are kept at various percentages in each of the sample. The tests have shown positive results and gives a scope of further practical implementations. The basic objective of the test is to find out the optimum percentage of plastic waste which can overrule the bitumen content in the mix for the design of flexible pavements. The basic intention behind this study is to replace bitumen by a conventional and non-biodegradable material which is the plastic waste.

Tarring pebbles have been used by Native Americans of southern California for thousands of years to melt, apply, and spread asphaltum. Although tarring pebbles are frequently observed in the archaeological record, they are seldom analyzed. In this study, we use size to construct a classification and typology of tarring pebbles found at three archaeological sites on San Nicolas Island, California. Three separate tarring pebble clusters exhibit particular characteristics that are distinct from one another. Our research suggests that tarring pebbles with specific attributes were being targeted for distinct purposes, allowing us to construct a classification based on pebble size.

Gilsonite, a naturally occurring asphaltite bitumen, consists of a complex mixture of organic compounds. In the present study, advanced one and two dimensional solid state and solution 1H, 13C and 15N nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) were employed to investigate its composition and structure. 13C NMR yielded a carbon aromaticity of 27%. Aromatic moieties in gilsonite were primarily single rings or small clusters of fused rings. Half of the aromatic carbons of gilsonite can be accounted for by pyrroles. 15N and 13C cross polarization-magic angle spinning (CP-MAS) NMR showed that most nitrogen in gilsonite was pyrrolic. The aromatic rings were heavily substituted with alkyl chains, as evidenced by 1Hsingle bond13C correlation spectra. Advanced solid state NMR spectral editing techniques clearly identified specific functional groups such as CCH3, CCH2, and Cdouble bond; length as m-dashCH2 (exomethylene). 1Hsingle bond13C wideline separation (WISE) NMR helped identify mobile and non-protonated alkyl carbons. FT-ICR-MS indicated that ∼64% of calculated formulae generated by ESI were aliphatic, while only about 0.8–2.5% of formulae contained possible aromatic rings. All of the assigned formulae contained at least one heteroatom (N, O or S), indicating that ionization by ESI was selective for the polar fraction of gilsonite and potentially less reflective of the overall chemical character of gilsonite than NMR spectroscopy. By combining the information obtained from advanced NMR and ultrahigh resolution MS we propose a structural model for gilsonite as a mixture of many pyrrolic and a few fused aromatic rings highly substituted with and connected by mobile aliphatic chains.

An analysis of paints found in ceramic sherd palettes from the 18th Dynasty (1548-1302 BCE) Pharaonic town on Sai Island in Upper Nubia using polarised light microscopy and infrared spectroscopy revealed pigments from the standard Egyptian repertoire: red and yellow ochres, Egyptian blue, calcite, gypsum, anhydrite, and the bright white huntite. Orange-yellow residues in ceramic sherds from the town were analysed using gas chromatography mass spectrometry (GC-MS) and were identified as Pistacia sp. resin, probably for use as incense. A dark organic substance from a vessel in the elite Pharaonic cemetery of the island was analysed using a second GC-MS method and was shown to be bitumen. Biomarkers in the bitumen indicate that its source may be the same as a sample from another Pharaonic town in Upper Nubia, suggesting a possible Nubian source. This is one of the earliest identifications of the use of bitumen in a funerary context in the ancient Nile Valley, and the furthest southern example yet analysed. Black fluids containing bitumen were used in Egypt as part of the process of mummification and for funerary anointing rituals; it is likely that the bitumen material at Sai was related to these practices.

In this study, the effects of addition of waste polyethylene on asphalt binder and asphalt concrete mixture properties were studied. Four asphalt concrete mixtures (each mixture containing different percentages of shredded polyethylene material) were prepared and tested as per Indian specifications. Shredded polyethylene and hot asphalt binder were added to heated aggregate (in same sequence) until all aggregates were coated. The loose mixtures were compacted and tested for its mechanical and volumetric properties. Furthermore , compacted specimens were aged for short-and long-term conditions. The extracted binder from the aged and control mixtures was tested for its rheological properties using a dynamic shear rheometer. Mixtures containing shredded polyethylene showed improvement with respect to the Marshall strength, flow, and volumetric properties. The properties of recovered asphalt binder indicated that the addition of polyethylene improved complex modulus values and decreased phase angle values over range of frequencies.

The paper presents the results of a chemical analysis of black pigment used to decorate pottery from Late Neolithic Tell Sabi Abyad, northern Syria (c. 6100 cal BC). The pigment appears to be bitumen. A comparison with known reference samples from modern locations of bituminous sources in the Near East suggests that the bitumen used to paint ceramics at Tell Sabi Abyad came from at least two different source areas in northern Iraq. The bitumen-painted ceramics at Tell Sabi Abyad represent the earliest evidence attested so far of bitumen used as a pigment for pottery decoration.

During the Later Prehistory of the Euphrates and Tigris Rivers and adjacent regions, a great cultural spread took place during the Late/Terminal Ubaid phases of Southern Mesopotamia. In the Northern Mesopotamian regions, it happened during the immediate preLate Chalcolithic phases. Excavations in Southeastern Turkey prove a continuity of Ubaid cultural traits at least during the earlier phases of the local Late Chalcolithic (LC1). Two archaeological sites, Surtepe and Tilbes-Körche, close to the Birecik Dam area (Turkish Euphrates) are presented and evaluated here. Surtepe höyük, a 8 ha Late Ubaid settlement that provided Coba bowls, has levels with painted pottery from the late Late Chalcolithic 1 or earlier LC2 phases in an area of at least 4 hectares in south and southwestern slopes. The small site of Tilbes-Körche has probably a bigger interconnected structure and no simple isolated buildings. Among the stone foundations we identify at least one tripartite premise with a surface over 90 m2 and two bipar-tite buildings. From the largest excavated unit (H3-H10) was recovered a stamp seal depicting a crosshatching motif and another token/stamp seal with 8 incised lines. Within LC1 or a transitional phase between it and LC2, the 18% of the pottery found in the Tilbes-Körche buildings was painted and there is a huge abundance of unpainted bowls, which are about half the ceramic ensemble, many with traces of a wheel or slow-wheel, mass-produced bowls, various variants of LC1 flint scraped, and two bowls that most resemble the so-called "flower pots". Resumen Durante la prehistoria reciente de los ríos Éufrates y Tigris y regiones adyacentes, una gran expansión cultural tuvo lugar durante las fases tardías y terminales de Ubaid del sur de Mesopotamia. En las regiones del norte de Mesopotamia, aconteció durante las fases previas del Calcolítico Final. Excavaciones en partes del sureste de Turquía demuestran la continuidad de los rasgos culturales Ubaid, al menos durante las fases más tempra-nas del Calcolítico Final 1 (LC1) local. Aquí se presentan y evalúan algunos sitios arqueológicos, Tilbes Höyük, Tilbes-Körche y Surtepe, cerca del área de la presa Birecik (Éufrates turco). Surtepe höyük, un asentamiento de 8 ha del Ubaid Final que proporcionó cuencos tipo Coba, tiene niveles con cerámicas pintadas de la fase final del LC1 o de comienzos del LC2 en un área de al menos 4 ha en las laderas sur y suroeste. El pequeño asentamiento de Tilbes-Körche tiene probablemente una gran estructura interconectada y no simples edificios aislados. Entre los cimientos de piedra identificamos al menos uno tripartito con una superficie de más de 90 m 2 y dos edificios bipartitos. En la unidad excavada más grande (H3-H10) se recuperó un se-llo que representa un motivo de rayado cruzado y otro sello o token con ocho líneas incisas. Dentro del LC1 o