Orpiment Research Articles

Comparative pharmaceutical evaluation of different samples of Yellow orpiment (Haratala) and Ayurvedic mineral formulation (Rasamanikya)

Background: The present work aimed to study the Physical and Physico-chemical Properties of raw Haratala (Yellow Orpiment), processed Haratala, and its self-prepared formulation Rasamanikya with different market preparations of Rasamanikya by using advance methods such as ICP-AES (qualitative and quantitative analysis), XRD and FEGSEM so that the particle size and elemental content can be estimated and compared in all the samples. This is an attempt to study the classical method of preparation as well as effect of purification process on the constituents of the drug and their size. Methods: Raw Patra Haratala (Orpiment) and three different samples of Rasamanikya were procured from authentic sources. Shodhana (purification) of Haratala was conducted by two different methods. Rasamanikya was prepared from the Haratala processed by two different methods. All the eight samples were subjected to physicochemical analysis, ICPAES, XRD and FEGSEM. Results: Arsenic content is decreased in all the samples except CSH in comparison with ASH. In ICPAES, number of elements is reduced in CSH, KSH and RMCSH in comparison with ASH whereas it is increased in RMKSH, RMMSA, RMMSB, and RMMSC. XRD analysis reveals that Average Crystal Size is minimum in RMMSA and maximum in RMMSC. Average Lattice Strain is minimum in ASH and maximum in RMMSC. Orpiment was detected in all the samples except RMKSH, RMMSB and RMMSC. FEG SEM indicates that the gross particle size of all the samples varies from 1um to 100nm at resolution ranging from 200 to 100000 magnifications. The nanoparticles are visualized at 50000 to 100000 magnifications. Conclusion: Advanced techniques like ICPAES, XRD and FEGSEM are very helpful in estimating the heavy metal content and particle size in Ayurvedic medicine. It is necessary from safety point of view. Small size particles increase the absorption of the drug in the body which causes increase in the bioavailability and potency of the drug. Hence the dose of the formulation may be reduced. Thereby the untoward effects of the high doses can be avoided.

Stability of modified technetium-containing magnesium potassium phosphate matrix under repository conditions with regard to biogeochemical effects

In this work, the biological stability of magnesium potassium phosphate (MPP) matrix was assessed for the first time under conditions modelling near-surface and deep repositories of radioactive waste (RW) containing technetium. It was found that MPP-matrix is potentially susceptible to microbial degradation, so it is necessary to introduce modifying additives. The efficiency of introduction of modifying additives - tetraphenylphosphonium chloride (TPP), thiourea (THIO), polyhexamethyleneguanidine hydrochloride (PHMG), polyethyleneimine (PEI), shungite (SHU), chalcopyrite (CP), orpiment (ORP) at immobilisation of pertechnetate ion in MPP-matrix has been estimated. The mechanical strength and water resistance of the obtained compounds were investigated. The maximum leaching rate of technetium was found to be 0.34 g cm-2 day-1 from the blank sample without additives. The addition of ORP and PHMG reduces the leaching rate of technetium by 90% and 62%, respectively, relative to the pure sample. The addition of other modifying additives reduced the leaching rate of pertechnetate ions by 15–25% on average. At the same time, the addition of PEI and THIO led to a decrease in compressive strength below the standard requirement of 4.9 MPa.a. Samples containing PHMG and ORP up to 0.5 wt% showed higher safety margin compared to the blank sample. ORP, PHMG and TPP can be proposed as modifying additives to reduce microbial activity during immobilisation of pertechnetate ion using MPP matrix.

A multi-analytical approach for the characterization of materials, manufacturing process and damage mechanisms of wall paintings in Samye Temple, Tibet

This research focuses on the multi-technique characterization and identification of degradation mechanisms of the wall paintings at the Samye Temple in Tibet, which is considered the first built temple of Tibetan Buddhism with an enormous cultural significance to the region. Wall painting general stratigraphy was thoroughly analyzed by Optical Microscopy (OM), Scanning Electron Microscopy – Energy Dispersive X-Ray Spectroscopy (SEM-EDS) and X-ray Powder Diffraction (XRD). Results reveal a clear sequence, from the interior to the surface, consisting on an adobe wall support, a coarse mud plaster, a fine mud plaster, a white ground layer, a surface paint layer, and a coating layer. The identification of natural and/or synthetic pigments and possible re-painted areas was analyzed by polarized light microscope and SEM-EDS, and subsequently studied using Raman spectroscopy. Results reveal the mineral pigments include red cinnabar (HgS) and red lead (Pb3O4), blue azurite (Cu3(CO3)2(OH)2), green malachite (Cu2CO3(OH)2), yellow orpiment (As2S3), and a gold layer (gold powder). White and black pigments are magnesite (MgCO3) and carbon, respectively. Additionally, the external surface coating varnish found on the top of the paint layer was also analyzed by Transmission Fourier Transform Infrared Spectroscopy with Attenuated Total Reflectance mode (FTIR-ATR), Proton Nuclear Magnetic Resonance (H1 NMR), Thermogravimetric analysis (TG), Mass Spectrometry (MS) and SEM-EDX analysis. Results show main components of this coating include acrylates and, possibly, silanes, revealing a recent conservation intervention activity. The hydric expansion/contraction of clay minerals in the adobe support and mud plaster layers and the rigid and impervious acrylate coating layer could have accelerated the deterioration and be the responsible for the development of cracks both at the interface of the different support layer and normal to the wall painting surface, resulting in massive losses. These findings are relevant to better understand the traditional manufacturing process of historic wall paintings in Tibet, which is not fully understood yet, and serve to further conservation activities of this historically rich temple.

The “Exultet 1” of Bari: multi-methodological approach for the study of a rare medieval parchment roll.

A rare medieval parchment roll, called Exultet 1 (first half of XI Century), preserved in the Diocesan Museum of Capitolo Metropolitano of Bari (Italy) has been studied. Certainly, it is one of the highest literary and artistic expressions ever produced in Bari, one of a kind. It is also the very first among medieval European liturgical rolls, in which miniatures are painted upside-down in respect to the text. To analyse inorganic pigments, a mobile laboratory has been set up at the museum. The techniques used, for a non-invasive and non-destructive in situ analysis, were: VIS-NIR spectrophotometry in reflectance mode with optic fibres (FORS), X-Ray fluorescence spectrometry (XRF) and finally µ-Raman spectroscopy. Such multi-methodological approach allowed to acquire many data without causing any stress to the artwork. The mineral pigments have been identified mainly by FORS and they are: red earth and minium, lapis lazuli and azurite, green earth and copper resinate, orpiment and yellow earth. In some areas, traces of a residual gold leaf have been identified by XRF. The presence of rare and precious pigments as lapis lazuli and gold leaf underlines the sacredness and the importance of the parchment. This is the first scientific investigation performed on the Exultet 1 of Bari.

Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues

Yellow orpiment (As2S3) and red–orange realgar (As4S4) photo-degrade and the nineteenth-century pigment emerald green (Cu(C2H3O2)2·3Cu(AsO2)2) degrades into arsenic oxides. Because of their solubility in water, arsenic oxides readily migrate and are found throughout the multi-layered paint system. The widespread arsenic migration has consequences for conservation, and this paper provides better insight into the extent of the problem. Five paint samples containing orpiment, realgar or emerald green pigments deriving from paintings by De Heem (17th C), Van Gogh (19th C), Rousseau (19th C), an unknown 17th C northern European artist and an Austrian painted cupboard (19th C) were investigated using SEM/EDX, imaging ATR-FTIR and arsenic (As) K–edge μ-XANES to obtain the spatial distribution and chemical speciation of arsenic in the paint system. In all of the samples investigated arsenic had migrated throughout the multi-layered paint structure of the art object, from support to varnish. Furthermore, As5+-species were found throughout the entire paint sample. We hypothesize that arsenic trioxide is first formed, dissolves in water, further oxidizes to arsenic pentaoxide, and then reacts with lead, calcium and other ions and is deposited in the paint system as insoluble arsenates. Since the degradation of arsenic pigments such as orpiment, realgar and emerald green occurs through a highly mobile intermediate stage, it not only affects the regions rich in arsenic pigments, but also the entire object, including substrate and top varnish layers. Because of this widespread potential for damage, preventing degradation of arsenic pigments should be prioritized and conservators should minimize exposure of objects containing arsenic pigments to strong light, large fluctuations in relative humidity and water-based cleaning agents.

Polymetallic mineralization of the Boranja orefield, Podrinje Metallogenic District, Serbia: zonality, mineral associations and genetic features

In the Serbo-Macedonian Metallogenetic Province, which is a part of the Alpine metallogenic unit, the ore deposits lie in number geotectonic units; they embrace part of the Vardar Zone, Serbo-Macedonian massif, and a small part of the Dinarides. This metallogenic province has been delineated mostly by reference to the Neogene metallogeny, related predominantly to granodiorite magma. These deposits include the most significant Pb-Zn and Sb deposits in Serbia, as well as smaller Bi, Mo, Cu, Fe, Sn, Au and minor U, W and Hg deposits. The Podrinje Metallogenic District belongs to the Serbo-Macedonian Metallogenetic Province. Smaller metallogenic provinces are isolated within the scope of the following orefields: Cer (Northwest Serbia), Boranja (West Serbia), and Srebrenica (East Bosnia & Herzegovina). Polymetallic deposits in the Boranja orefield are genetically related to the emplacement of a Tertiary granodiorite complex. It consists primarily of a large number of sulfide deposits with Pb-Zn, and Sb; with subordinate Cu, As, Bi and Ag. Among them, the presence of small magnetite deposits, connected to the pyrometasomatic (skarn) stage is significant. Skarns are of calcic type, and were formed along contacts of Triassic limestones and quartz diorites. Ore minerals are similar among the various types of orebodies in the Boranja orefield and consist of sulfides (pyrrhotite, pyrite, marcasite, chalcopyrrhotite, chalcopyrite, cubanite, mackinawite, valleriite, covelline, chalcocite, bismuthinite, molybdenite, sphalerite, mercurian sphalerite, greenockite, galena, arsenopyrite, stibnite, duranusite, realgar, orpiment, cinnabar, metacinnabar); sulfosalts (bursaite, cannizzarite, cosalite, aikinite, ustarasite, tetradymite, ferrian tetrahedrite, argentian tetrahedrite, pyrargyrite, diaphorite, freieslebenite, schirmerite, fizelyite, stannite, jamesonite, boulangerite, bournonite, As-bournonite, falkmanite, zinkenite, fuloppite, robinsonite, plagionite, twinnite, geocronite, gratonite); telluride (calaverite); native metals and alloys (gold, silver, electrum, bismuth, arsenic); oxides and complex-oxides (magnetite, hematite, rutile, anatase, scheelite, powellite, valentinite, senarmontite, kermesite, adamite, arsenolite); and gangue minerals (silicates, carbonates, fluorite, calcite, siderite, Mn-Zn siderite, fluorite, apatite, barite, dolomite, anglesite, cerussite, smithsonite, otavite, malachite, azurite, scorodite, quartz, limonite, organic matter). Minerals of the titled orefield were formed in several successive stages, which together correspond to a unique cycle of mineralization that is genetically related to the subvulcanic-plutonic intrusion of the Neogene-aged magmatic Boranja complex. Mineral associations, which have spatial-zonal arrangement, are rhythmically developed from the Tertiary granodiorite of Boranja to outside surroundings: A) Fe-Cu(Bi) belt → B) Pb(Ag)-Zn belt → C) Sb(As) belt → D) CaF 2 (Pb-Zn) belt.

Ore-fluid evolution at the Getchell Carlin-type gold deposit, Nevada, USA

Minerals and fluid-inclusion populations were examined using petrography, microthermometry, quadrupole mass-spectrometer gas analyses and stable-isotope studies to characterize fluids responsible for gold mineralization at the Getchell Carlin-type gold deposit. The gold-ore assemblage at Getchell is superimposed on quartz-pyrite vein mineralization associated with a Late-Cretaceous granodiorite stock that intruded Lower-Paleozoic sedimentary rocks. The ore assemblage, of mid-Tertiary age, consists of disseminated arsenian pyrite that contains submicrometer gold, jasperoid quartz, and later fluorite and orpiment that fill fractures and vugs. Late ore-stage realgar and calcite enclose ore-stage minerals. Pre-ore quartz trapped fluids with a wide range of salinities (1 to 21 wt.% NaCl equivalent), gas compositions (H2O, CO2, and CH4), and temperatures (120 to > 360°C). Oxygen- and hydrogen-isotope ratios indicate that pre-ore fluids likely had a magmatic source, and were associated with intrusion of the granodiorite stock and related dikes. Ore-stage jasperoid contains moderate salinity, aqueous fluid inclusions trapped at 180 to 220°C. Ore fluids contain minor CO2 and trace H2S that allowed the fluid to react with limestone host rocks and transport gold, respectively. Aqueous inclusions in fluorite indicate that fluid temperatures declined to ∼ 175°C by the end of ore-stage mineralization. As the hydrothermal system collapsed, fluid temperatures declined to 155 to 115°C and realgar and calcite precipitated. Inclusion fluids in ore-stage minerals have high δDH2O and δ18OH2O values that indicate that the fluid had a deep source, and had a metamorphic or magmatic origin, or both. Late ore-stage fluids extend to lower δH2O values, and have a wider range of δ18OH2O values suggesting dilution by variably exchanged meteoric waters. Results show that deeply sourced ore fluids rose along the Getchell fault system, where they dissolved carbonate wall rocks and deposited gold-enriched pyrite and jasperoid quartz. Gold and pyrite precipitated together as H2S in the ore fluids reacted with iron in the host rocks. As ore fluids mixed with local aquifer fluids, ore fluids became cooler and more dilute. Cooling caused precipitation of ore-stage fluorite and orpiment, and late ore-stage realgar. Phase separation and/or neutralization of the ore fluid during the waning stages of the hydrothermal ore system led to deposition of late ore-stage calcite.

Some manuscripts in Grantha script in Bangkok

Among the manuscripts in the National Library in Bangkok are a number of sმmut dam ‘blank books’ written in yellow orpiment on blackened paper. Many of these are in Thai, but a few, catalogued under the number XVII 37 are in two scripts that show very close affinities with South Indian Grantha.

Treatment of surra by atoxyl and orpiment

Treatment of surra by atoxyl and orpiment

Occurrence of realgar and orpiment in Utah

Occurrence of realgar and orpiment in Utah

Of a remarkable spring, about Paderborn in Germany

An inquiring gentleman of those parts writes to his friend in London, as follows; In this diocess of Paderborn, about 2 leagues from that town, is a treble spring call'd Metborn, which has three streams, two wherof are not above one foot and a half distant from one another, and yet of so differing qualities, that whereas one of them is limpid, blewish, lukewarm, bubling, and holding sal-armoniack, ochra, iron, vitriol, allum, sulphur, niter, orpiment, used against epilepsies, bad spleens, and the wormes;