Nicholas Crisp's “Porcellien”: A petrological comparison of sherds from the Vauxhall (London; ca. 1751–1764) and Indeo Pottery (Bovey Tracey,Devonshire; ca. 1767–1774) factory sites

The character of porcelain wares made by Nicholas Crisp early and late in his career was assessed using microchemical and petrographic data for sherds excavated from the sites of the factories he operated at Vauxhall and Bovey Tracey. The results indicate that, over time, Crisp increasingly made use of diverse types of pastes as he struggled to produce a commercially viable line of porcelain. Based on the analysis of a limited number of samples, he appears to have largely restricted himself at Vauxhall to using soapstone (Mg‐rich)‐ and flint‐glass (Pb‐rich) frit‐bearing pastes that varied in the amount of calcite they contained. He also experimented with Mg+Pb‐rich pastes at Bovey Tracey, but included a novel ingredient (barite) and varied the proportion of other minor constituents (e.g., bone ash), apparently in an effort to resolve some of the firing problems that plagued him at Vauxhall. In addition, Crisp appears to have produced bone ash (phosphatic) porcelain at Bovey Tracey, and, in collaboration with William Cookworthy, the proprietor of the Plymouth factory, fired a range of true porcelain (Si+Al‐rich) pastes. Bulk compositional data indicate that Crisp's diopside‐bearing Mg+Pb‐rich wares were derived from pastes containing talc and calcite rather than dolomite. The mineralogy of these and some contemporary magnesian/plombian porcelains are interpreted using the SiO₂‐CaO‐MgO phase diagram. This diagram shows that these wares can form and preserve diopside (Ca‐Mg silicate) given suitable bulk CaO contents and kiln‐firing temperatures. Phosphatic sherds from Bovey Tracey are compositionally distinct (lower SiO₂ and higher Al₂O₃ and bone‐ash components) from a single bone‐ash sample from Vauxhall, indicating that Crisp experimented with novel bone‐ash pastes, and was not positively influenced by the Vauxhall phosphatic recipe, if indeed one existed. True porcelains from Bovey Tracey have more extreme SiO₂/Al₂O₃ ratios (= 2.0 [two sherds]; 4.5 [one sherd]) than their Plymouth/Bristol counterparts (SiO₂/Al₂O₃ = 2.3–3.0). Collectively, the analytical data underscore the experimental—and ultimately unsuccessful—character of the diverse wares produced by Nicholas Crisp. © 2000 John Wiley & Sons, Inc.     

Geochemical and mineralogical distinctions between Bonnin and Morris (Philadelphia, 1770–1772) porcelain and some contemporary British phosphatic wares

The major element compositions of 15 ceramic sherds from the Bonnin and Morris factory site were determined by electron microprobe. Thirteen samples are phosphatic; the others consist of (a) “soapstone” (magnesian/plombian) and (b) true porcelain, and are interpreted as exotic artifacts, as is one compositionally distinct (relatively SiO₂‐poor, P₂O₅+CaO‐rich) phosphatic sample. Although long considered to be virtually indistinguishable from Bow porcelain (London: ca. 1747–1776), the phosphatic Philadelphia wares have a relatively low mean CaO/P₂O₅ ratio (3.3 versus 3.8; molecular proportions) and high alumina content (6.6 versus 5.4 wt % Al₂O₃). Furthermore, unlike Bow, the Bonnin and Morris samples contain calcic plagioclase (bytownite), and in some instances, an orthoclase‐rich ternary feldspar. The preservation of calcic plagioclase indicates that Philadelphia porcelain was fired at (rather than above) the thermal minimum in the An‐SiO₂‐C₃P system, although the presence of Na (and other fluxes) in these wares precludes the exact determination of the maximum firing temperature from this phase diagram. These wares are also distinctive insofar as the phosphate and melt phases can contain small amounts of lead; they have bulk lead contents of approximately 0.1–1.2 wt % PbO. This component has not been detected in the body of Bow or other contemporary British phosphatic porcelains. Their principal similarity lies in the fact that both wares contain sulfate. In addition, the glazes on Bonnin and Morris porcelain (e.g., PbO ∼ 35–50 wt %; SnO₂ ∼ 1–2%) compositionally resemble those used at Bow. If feldspar is formed at all, then Al‐poor phosphatic porcelain (or those with low CaO/P₂O₅ ratios) will have comparatively low modal calcic plagioclase contents, thereby allowing the rapid depletion of this mineral via resorption by the melt phase during vitrification. Such appears to have been the case for analyzed Bow porcelain, which is therefore interpreted to have been overfired (sensu lato) relative to its Philadelphia counterpart. Conceivably, calcic plagioclase could be preserved in low‐Al wares that were fired only briefly at vitrification temperatures. Given the role of firing history in governing the mineralogy of porcelain, compositional criteria are more reliable for distinguishing these wares. © 2001 John Wiley & Sons, Inc.     

Fayalite-sekaninaite paralava from the Ravat coal fire (central Tajikistan)

We studied ferrous paralava, a high-temperature rock, produced by complete fusion of the sedimentary protolith in the Ravat natural coal fire which has been on for over two thousand years. The paralava was sampled from the Fan-Yagnob coal deposit at the Kukhi-Malik site in the vicinity of former Ravat Village in central Tajikistan. This rock contains fayalite, sekaninaite, hercynite, Ti-magnetite, tridymite, and siliceous glass. Low-Ca pyroxene (clinoferrosilite), globules of sulfides (mainly pyrrhotite) and Fe-Ti oxides, secondary greenalite (after fayalite) and hematite are minor. Paralava includes xenoliths of partially molten clinkers (up to 20 vol.%) composed of mullite, cordierite, tridymite, and relict detrital quartz. We found relatively high Fe contents (100?Fe/(Fe+Mg) > 60) in mafic minerals, high K₂O enrichment (up to 1.4 wt.%) in sekaninaite, and an unusually low CaO content (0.5 wt.%) in the rock. The Ravat paralava appears to be derived from a mixture of pelitic rocks (50–70%) and iron-rich rocks (30–50%), but without participation of calcareous material, which explains the low CaO and the absence of plagioclase and Ca-bearing pyroxene. The primary melt was as hot as >1210 °C, and the coal-fired fayalite-sekaninaite paralava crystallized at 1200–1100 °C, at a relatively low oxygen fugacity (near the QFM buffer), outside the zone of active aeration. Large-scale crystallization of ferrospinels and fayalite led to increasing Al₂O₃ and SiO₂ in the melt whence sekaninaite and tridymite crystallized as later phases. The residual melt progressively acquired a more silicic-aluminous composition, rich in K₂O, CaO, and P₂O₅, and became quenched to glass at >1080–1090 °C, when temperature dropped abruptly, possibly, by roof collapse or opening of large cracks, as it usually happens in underground coal fires.     

From London to Liverpool: Evidence for a Limehouse–Reid porcelain connection based on the analysis of sherds from the Brownlow Hill (ca. 1755–1767) factory site

The diversity of Brownlow Hill porcelains of the W^m Reid & Co. era is due to the remarkably wide range in the composition of their pastes and glazes and inferred firing conditions relative to the initial vitrification temperature. Sixteen of 21 analyzed sherds from the factory site are bone‐ash wares that display large variations in their bulk chemical composition. The remaining samples have silicious‐aluminous (akin to “stone china” sensu Richard Pococke in 1750) and silicious‐aluminous‐calcic (“S‐A‐C”) compositions that resemble Limehouse (London) and Pomona (Staffordshire) porcelains produced during the 1740s. The mineralogy of the Brownlow Hill S‐A‐C sherds suggests firing at a relatively high temperature (T_max approaching 1400°C, based on relations on the SiO₂‐Al₂O₃‐CaO phase diagram), thereby obscuring the identity of some of the ingredients (e.g., the source of CaO) used in their manufacture. Limehouse and Brownlow Hill may have been linked through the activities of William Ball, who is mentioned in connection with both factories, or indirectly via former Limehouse staff later employed at the Pomona factory, located not far from a W^m Reid & Co. branch factory in Shelton, Stoke‐on‐Trent. In terms of a time line, knowledge of these pastes appears to have spread first from London to Staffordshire, and then to Liverpool. © 2003 Wiley Periodicals, Inc.     

Evidence for extreme fractionation of peralkaline silicic magmas, the Boseti volcanic complex, Main Ethiopian Rift

Matrix glass and melt inclusions in phenocrysts from pantellerite lavas of the Boseti volcanic complex, Ethiopia, record extreme fractionation of peralkaline silicic magma, with Al₂O₃ contents as low as 2.3?wt.%, FeO* contents up to 17?wt.% and SiO₂ contents ~65?wt.%. The new data, and published data for natural and experimental glasses, suggest that the effective minimum composition for peralkaline silicic magmas has ~5?wt.% Al₂O₃, 13?wt.% FeO* and 66?±?2?wt.% SiO₂. The dominant fractionating assemblage is alkali feldspar?+?fayalite?+?hedenbergite?+?oxides?±?quartz. Feldspar – melt relationships indicate that the feldspar is close to the minimum on the albite-orthoclase solid solution loop through the entire crystallization history. There is petrographic, mineralogical and geochemical evidence that magma mixing may have been a common process in the Boseti rhyolites.     

Mineralogy, conditions of crystallization and melt generation of epidote-bearing porphyries from the Middle Urals, Russian federation

Epidote-bearing porphyritic dikes (whole rock analysis: SiO₂?=?55–65 wt. %, MgO <2.1 wt. %, K₂O <2.5 wt. %, Al₂O₃ >17 wt. %, Na₂O + K₂O?=?5.7–9.4 wt. %) situated in the continental margin zone, the Middle Urals, Russian Federation have been dated using SHRIMP U-Pb zircon techniques and give a Middle Devonian age of 388?±?2 Ma and 389?±?6 Ma. The porphyries contain phenocrysts of magmatic epidote (Ps?=?17–25 %), Ca- and Mn-rich (CaO >9 wt. %; MnO >6 wt. %) almandine garnet, Al-rich (Al₂O₃?=?12–16 wt. %) amphibole, titanite, plagioclase, biotite, muscovite, apatite, and quartz. 60 to 70 % groundmass of the porphyritic dikes consists of fine-grained albite, quartz, and K-feldspar. A variety of thermobarometric estimations, plus comparison with published experimental data indicate that the phenocryst assemblage was stable between 5 and 11 kbar and 690 to 800 °C. Oxygen fugacity was close to or greater than logfo₂ = Ni-NiO + 1. Later stage formation of the quartz-feldspar groundmass took place at hypabyssal conditions, corresponding to 1 to 2 kbar and 660 to 690 °C. The porphyritic dikes are metaluminous to slightly peraluminous (ACNK?=?0.7–1.17). They are enriched in REE and depleted Nb and Ti. They show features typical of subduction-related magmas. Chemical composition and isotopic ratios of ⁸⁶Sr/⁸⁷Sr_i?=?0.709–0.720 suggest that both mantle- and deep crustal-derived materials were involved in their petrogenesis.     

Geochemistry,and zircon U–Pb and molybdenite Re–Os geochronology of Jilongshan Cu–Au deposit,southeastern Hubei Province,China

The Jilongshan skarn Cu–Au deposit is located at the Jiurui ore cluster region in the southwestern part of the Middle–Lower Yangtze River valley metallogenic belt. The region is characterized by NW‐, NNW‐ and EW‐trending faults and the mineralization occurs at the contact of lower Triassic carbonate rocks and Jurassic granodiorite porphyry intrusions. The intrusives are characterized by SiO₂, K₂O, and Na₂O concentrations ranging from 61.66 to 67.8 wt.%, 3.29 to 5.65 wt.%, and 2.83 to 3.9 wt.%, respectively. Their A/CNK (A/CNK = n(Al₂O₃)/[n(CaO) + n(Na₂O) + n(K₂O)]) ratio, δEu, and δCe vary from 0.77 to 1.17, 0.86 to 1, and 0.88 to 0.96, respectively. The rocks show enrichment in light rare earth elements ((La/Yb)_N = 7.61–12.94) and large ion lithophile elements (LILE), and depletion in high field strength elements (HFSE), such as Zr, Ti. They also display a peraluminous, high‐K calc‐alkaline signature typical of intrusives associated with skarn and porphyry Cu–Au–Mo polymetallic deposits. Laser ablation inductively coupled plasma spectrometry (LA‐ICP‐MS) zircon U–Pb age indicates that the granodiorite porphyry formed at 151.75 ± 0.70 Ma. A few inherited zircons with older ages (677 ± 10 Ma, 848 ± 11 Ma, 2645 ± 38 Ma, and 3411 ± 36 Ma) suggest the existence of an Archaean basement beneath the Middle–Lower Yangtze River region. The temperature of crystallization of the porphyry estimated from zircon thermometer ranges from 744.3 °C to 751.5 °C, and 634.04 °C to 823.8 °C. Molybdenite Re–Os dating shows that the Jilongshan deposit formed at 150.79 ± 0.82 Ma. The metallogeny and magmatism are correlated to mantle–crust interaction, associated with the subduction of the Pacific Plate from the east. Copyright © 2013 John Wiley & Sons, Ltd.     

The stability of sapphirine + quartz: calculated phase equilibria in FeO–MgO–Al2O3–SiO2–TiO2–O

The presence in rocks of coexisting sapphirine + quartz has been widely used to diagnose conditions of ultra‐high‐temperature (UHT) metamorphism (>900 °C), an inference based on the restriction of this assemblage to temperatures >980 °C in the conventionally considered FeO–MgO–Al₂O₃–SiO₂ (FMAS) chemical system. With a new thermodynamic model for sapphirine that includes Fe₂O₃, phase equilibra modelling using thermocalc software has been undertaken in the FeO–MgO–Al₂O₃–SiO₂–O (FMASO) and FeO–MgO–Al₂O₃–SiO₂– TiO₂–O (FMASTO) chemical systems. Using a variety of calculated phase diagrams for quartz‐saturated systems, the effects of Fe₂O₃ and TiO₂ on FMAS phase relations are shown to be considerable. Importantly, the stability field of sapphirine + quartz assemblages extends down temperature to 850 °C in oxidized systems and thus out of the UHT range.     

Stability of sapphirine + quartz in the oxidized rocks of the Wilson Lake terrane,Labrador: calculated equilibria in NCKFMASHTO

The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al₂O₃–SiO₂ (FMAS) system. However, the potential for sapphirine to contain significant Fe³⁺ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al₂O₃–SiO₂–TiO₂–O (FMASTO), expansion into K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H₂O and O contents to use in the modelled compositions are investigated using T–M_H2O and T–M_O pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.     

Mineralogy,geochemistry, and ore formation of Nuwaifa bauxite deposit,western desert of Iraq

Nuwaifa Formation is a part of sequence stratigraphy that belongs to the Jurassic system exposed in the western desert of Iraq. The Jurassic system consists of Ubaid, Hussainiyat, Amij, Muhaiwir, and Najmah formations. Each formation is composed of basal clastic unit overlain by upper carbonate unit. Nuwaifa karst bauxite was developed in fossil karsts within the Ubaid Formation in areas where maximum intersection of fractures and faults exist. This bauxitization process affected the upper surface of the Ubaid limestone formation, which directly underlies the Nuwaifa bauxite Formation. Nuwaifa Formation represents karst-filling deposit that consists of a mixture of allochthonous (sandstone, claystone, and mudstone) and autochthonous lithofacies (bauxite kaolinite, kaolinitic bauxite, iron-rich bauxite, and flint clay). Most bauxite bodies occur within the autochthonous lithofacies and are lenticular in shape with maximum thickness ranges from few meters to 35 m and in some place up to 100 m. Petrographically, the bauxite deposit exhibits collomorphic-fluidal, pisolitic, oolitic, nodular, brecciated, and skeletal textures indicative of authigenic origin. Mineralogy boehmite and gibbsite are the only bauxite minerals; the former is dominant in the upper parts of the bauxite profiles, whereas the latter is dominant throughout the lower and middle part of the bauxite. Kaolinite, hematite, goethite, calcite, and anatase occur to a lesser extent. The study bauxites are mainly composed of Al₂O₃ (33–69.6 wt.%), SiO₂ (8.4–42 wt.%), Fe₂O₃ (0.5–15.9 wt.%), and TiO₂ (0.7–6.1 wt.%) with LOI ranging from 13.5 to 19.1 wt.%. Geochemical investigations indicate that the immobile elements like Al₂O₃, TiO₂, Cr, Zr, and Ni were obviously enriched, while SiO₂, Fe₂O₃, CaO, MgO, Zn, Co, Ba, Mn, Cu, and Sr were depleted during bauxitization process. The results of this study strongly suggest that the bauxite deposits of the Nuwaifa Formation are derived from the kaolinite of the Lower Hussainiyat Formation.     

Geochemical systematics of the Mauranipur-Babina greenstone belt,Bundelkhand Craton,Central India:Insights on Neoarchean mantle plume-arc accretion and crustal evolution

The Neoarchean Bundelkhand greenstone sequences at Mauranipur and Babina areas within the Bundelkhand Gneissic Complex preserve a variety of magmatic rocks such as komatiitic basalts, basalts,felsic volcanic rocks and high-Mg andesites belonging to the Baragaon, Raspahari and Koti Formations.The intrusive and extrusive komatiitic basalts are characterized by low SiO_2(39-53 wt.%), high MgO(18-25 wt.%).moderately high Fe_2O_3(7.1-11.6 wt.%), Al_2O_3(4.5-12.0 wt.%), and TiO_2(0.4-1.23 wt.%)with super to subchondritic(Gd/Yb)N ratios indicating garnet control on the melts. The intrusive komatiitic suite of Ti-enriched and Al-depleted type possesses predominant negative Eu and positive Nb, Ti and Y anomalies. The chemical composition of basalts classifies them into three types with varying SiO_2, TiO_2, MgO, Fe_2O_3, Al_2O_3 and CaO. At similar SiO_2 content of type Ⅰ and Ⅲ basalts, the type II basalts show slightly high Al_2O_3 and Fe_2O_3 contents. Significant negative anomalies of Nb, Zr, Hf and Ti, slightly enriched LREE with relatively flat HREE and low ∑REE contents are observed in type Ⅰ and Ⅱ basalts. TypeⅢ basalts show high Zr/Nb ratios(9.8-10.4), TiO_2(1.97-2.04 wt.%), but possess strikingly flat Zr, Hf, Y and Yb and are uncontaminated. Andesites from Agar and Koti have high SiO_2(55-64 wt.%), moderate TiO_2(0.4-0.7 wt.%), slightly low Al_2O_3(7-11.9 wt.%), medium to high MgO(3-8 wt.%) and CaO contents(10-17 wt.%). Anomalously high Cr, Co and Ni contents are observed in the Koti rhyolites. Tholeiitic to calc alkaline affinity of mafic-felsic volcanic rocks and basalt-andesite dacite-rhyolite differentiation indicate a mature arc and thickened crust during the advanced stage of the evolution of Neoarchean Bundelkhand greenstone belt in a convergent tectonic setting where the melts were derived from partial melting of thick basaltic crust metamorphosed to amphibolite-eclogite facies. The trace element systematics suggest the presence of arc-back arc association with varying magnitudes of crust-mantle interaction. La/Sm, La/Ta,Nb/Th, high MgO contents(20 wt.%), CaO/Al_2O_3 and(Gd/Yb)_N 1 along with the positive Nb anomalies of the komatiite basalts reflect a mantle plume source for their origin contaminated by subductionmetasomatized mantle lithosphere. The overall geochemical signatures of the ultramafic-mafic and felsic volcanic rocks endorse the Neoarchean plume-arc accretion tectonics in the Bundelkhand greenstone belt.     

Calcic hydrosilicate metasomatic rocks at the Gumeshevsk skarn-porphyry copper deposit in the central Urals,Russia

The body of hydroxylellestadite metasomatic rock penetrated by a borehole drilled at the Gumeshevsk deposit at depths of 530–534 m includes a thin interval of younger lower temperature tobermorite-plombierite metasomatic rock with subordinate amounts of Ca-Si gel, tacherenite, cubic lime, and thaumasite. Hydroxylellestadite has never before been found in calc skarns. The hydroxylellestadite metasomatic rock is cut by gypsum and fukalite veinlets, and the tobermorite-plombierite metasomatic rock is intersected by thaumasite veinlets. The pristine rock of the metasomatics was marble, and the metasomatic rock replaced andradite-bearing wollastonite skarn (with wollastonite replaced by foshagite). The ore minerals (chalcopyrite, valleriite, sphalerite, and others) were formed after the hydroxylellestadite metasomatite but most probably before the tobermorite-plombierite metasomatic rock and the veinlets of calcic minerals. The metasomatic rock was produced at significant variations in the oxygen, sulfur, and carbon dioxide fugacities. The composition of the hydroxylellestadite is, according to its microprobe analysis, as follows (wt %): SiO₂ 17.10, TiO₂ 0.01, Al₂O₃ 0.02, FeO 0.20, MnO 0.00, MgO 0.04, CaO 55.40, Na₂O 0.14, K₂O 0.09, P₂O₅ 0.12, CO₂ 1.90 (chemical analysis), SO₃ 21.60, F 0.16, Cl 0.14, total 96.92. The plombierite (SiO₂ 43.8–44.1 wt %, CaO 30.5–31.1 wt %) in the metasomatic rock notably differs from rare plombierite (SiO₂ 48.18 wt %, CaO 39.19 wt %) contained in the veinlets of thaumasite (SiO₂ 12.70 wt %, CaO 30.69 wt %, SO₃ 17.78 wt %).     

Mineralogy and environmental geochemistry of historical iron slag,Hopewell Furnace National Historic Site,Pennsylvania, USA

The Hopewell Furnace National Historic Site in southeastern Pennsylvania, which features an Fe smelter that was operational in the 18th and 19th centuries, is dominated by three slag piles. Pile 1 slag, from the Hopewell Furnace, and pile 2 slag, likely from the nearby Cornwall Furnace, were both produced in cold-blast charcoal-fired smelters. In contrast, pile 3 slag was produced in an anthracite furnace. Ore samples from the nearby Jones and Hopewell mines that fed the smelter are mainly magnetite-rich with some sulfides (pyrite, chalcopyrite, sphalerite) and accessory silicates (quartz, garnet, feldspar, and clay minerals). Slag piles 1 and 2 are similar mineralogically containing predominantly skeletal and dendritic aluminian diopside and augite, skeletal forsteritic olivine, glass, rounded blebs of metallic Fe, and exotic quartz. Olivine is a major phase in all samples from pile 2, whereas it occurs in only a few samples from pile 1. Samples of the <2 mm-size fraction of surface composite slag material or crushed slag from at depth in piles 1 and 2 are mineralogically similar to the large surface slag fragments from those piles with the addition of phases such as feldspars, Fe oxides, and clay minerals that are either secondary weathering products or entrained from the underlying bedrock. Pile 3 slag contains mostly skeletal forsteritic olivine and Ti-bearing aluminian diopside, dendritic or fine-grained subhedral melilite, glass, euhedral spinel, metallic Fe, alabandite–oldhamite solid solution, as well as a sparse Ti carbonitride phase. The bulk chemistry of the slag is dominated by Al₂O₃ (8.5–16.2 wt.%), CaO (8.2–26.2 wt.%), MgO (4.2–24.7 wt.%), and SiO₂ (36.4–59.8 wt.%), constituting between 81% and 97% of the mass of the samples. Piles 1 and 2 are chemically similar; pile 1 slag overall contains the highest Fe₂O₃, K₂O and MnO, and the lowest MgO concentrations. Pile 3 slag is high in Al₂O₃, CaO and S, and low in Fe₂O₃, K₂O and SiO₂ compared to the other piles. In general, piles 1 and 2 are chemically similar to each other, whereas pile 3 is distinct – a conclusion that reflects their mineralogy. The similarities and differences among piles in terms of mineralogy and major element chemistry result from the different smelting conditions under which the slag formed and include the fuel source, the composition of the ore and flux, the type of blast (cold versus hot), which affects the furnace temperature, and other beneficiation methods.     

Evolution of the trachydacite and pantellerite magmas of the bimodal volcanic association of Dzarta-Khuduk, Central Mongolia: Investigation of inclusions in minerals

Using various methods of melt inclusion investigation, including electron and ion microprobe techniques, we estimated the composition, evolution, and formation conditions of melts producing the trachydacites and pantellerites of the Late Paleozoic bimodal volcanic association of Dzarta-Khuduk, Central Mongolia. Primary crystalline and melt inclusions were detected in anorthoclase from trachydacites and quartz from pantellerites and pantelleritic tuffs. Among the crystalline inclusions, we identified hedenbergite, fluorapatite, and pyrrhotite in the trachydacites and F-arfvedsonite, fluorite, ilmenite, and the rare REE diorthosilicate chevkinite in the pantellerites. Melt inclusions in anorthoclase from the trachydacites are composed of glass, a gas phase, and daughter minerals (F-arfvedsonite, fluorite, villiaumite, and anorthoclase rim on the inclusion wall). Melt inclusions in quartz from the pantellerites are composed of glass, a gas phase, and a fine-grained salt aggregate consisting of Li, Na, and Ca fluorides (griceite, villiaumite, and fluorite). Melt inclusions in quartz crystalloclasts from the pantelleritic tuffs are composed of homogeneous silicate glasses. The phenocrysts of the trachydacites and pantellerites crystallized at temperatures of 1060–1000°C. During thermometric experiments with quartz-hosted melt inclusions from the pantellerites, the formation of immiscible silicate and salt (fluoride) melts was observed at a temperature of 800°C. Homogeneous melt inclusions in anorthoclase from the trachydacites have both trachydacite and rhyolite compositions (wt %): 68–70 SiO₂, 12–13 Al₂O₃, 0.34–0.74 TiO₂, 5–7 FeO, 0.4–0.9 CaO, and 9–12 Na₂O + K₂O. The agpaitic index ranges from 0.92 to 1.24. The glasses of homogenized melt inclusions in quartz from the pantellerites and pantelleritic tuffs have rhyolitic compositions. Compared with the homogeneous glasses trapped in anorthoclase of the trachydacites, quartz-hosted inclusions from the pantellerites show higher SiO₂ (72–78 wt %) and lower Al₂O₃ contents (7.8–10.0 wt %). They also contain 0.14–0.26 wt % TiO₂, 2.5–4.9 wt % FeO, 9–11 wt % Na₂O + K₂O, and 0.9–0.15 wt % CaO and show an agpaitic index of 1.2–2.05. Homogeneous melt inclusions in quartz from the pantelleritic tuffs contain 69–72 wt % SiO₂. The contents of other major components, including TiO₂, Al₂O₃, FeO, and CaO, are close to those in the homogeneous glasses of quartzhosted melt inclusions in the pantellerites. The contents of Na₂O + K₂O are 4–10 wt %, and the agpaitic index is 1.0–1.6. The glasses of melt inclusions from each rock group show distinctive volatile compositions. The H₂O content is up to 0.08 wt % in anorthoclase of the trachydacites, 0.4–1.4 wt % in quartz of the pantellerites, and up to 5 wt % in quartz of the pantelleritic tuffs. The content of F in the glasses of melt inclusions in the phenocrysts of the trachydacites is no higher than 0.67 wt %, and up to 1.4–2.8 wt % in quartz from the pantellerites. The Cl content is up to 0.2 wt % in the glasses of melt inclusions in the minerals of the trachydacites and up to 0.5 wt % in the glasses of quartz-hosted melt inclusions from the pantellerites. The investigation of trace elements in the homogenized glasses of melt inclusions in minerals showed that the trachydacites and pantellerites were formed from strongly evolved rare-metal alkaline silicate melts with high contents of Li, Zr, Rb, Y, Hf, Th, U, and REE. The analysis of the composition of homogeneous melt inclusions in the minerals of the above rocks allowed us to distinguish magmatic processes resulting in the enrichment of these rocks in trace and rare earth elements. The most important processes are the crystallization differentiation and immiscible separation of silicate and fluoride salt melts. It was also shown that all the melts studied evolved in spatially separated magma chambers. This caused the differences in the character of melt evolution between the trachydacites and pantellerites. During the final stages of differentiation, when the magmatic system was saturated with respect to ore elements, Na-Ca fluoride melts were separated and extracted considerable amounts of Li.     

Garnet and spinel lherzolite assemblages in MgO–Al2O3–SiO2 and CaO–MgO–Al2O3–SiO2: thermodynamic models and an experimental conflict

The recent publication of an updated thermodynamic dataset for petrological calculations provides an opportunity to illustrate the relationship between experimental data and the dataset, in the context of a new set of activity–composition models for several key minerals. These models represent orthopyroxene, clinopyroxene and garnet in the system CaO–MgO–Al₂O₃–SiO₂ (CMAS), and are valid up to 50 kbar and at least 1800 °C; they are the first high‐temperature models for these phases to be developed for the Holland & Powell dataset. The models are calibrated with reference to phase‐relation data in the subsystems CaO–MgO–SiO₂ (CMS) and MgO–Al₂O₃–SiO₂ (MAS), and will themselves form the basis of models in larger systems, suitable for calculating phase equilibria in the crust and mantle. In the course of calibrating the models, it was necessary to consider the reaction orthopyroxene + clinopyroxene + spinel = garnet + forsterite in CMAS, representing a univariant transition between simple spinel and garnet lherzolite assemblages. The high‐temperature segment of this reaction has been much disputed. We offer a powerful thermodynamic argument relating this reaction to the equivalent reaction in MAS, that forces us to choose between good model fits to the data in MAS or to the more recent data in CMAS. We favour the fit to the MAS data, preserving conformity with a large body of experimental and thermodynamic data that are incorporated as constraints on the activity–composition modelling via the internally consistent thermodynamic dataset.     

Microstructures of phosphatic porcelain from sintering to vitrification: Evidence from sherds excavated in Charleston,South Carolina

Eight phosphatic porcelain sherds recovered from various historical sites in Charleston were analyzed by electron microprobe. Some sherds contain sulfur (2.3–3.1wt.% SO₃); others contain only traces of this component. The analytical data suggest that the sulfurous sherds are Bow porcelain (London, Bowcock period, ca. 1755–1769). The origin(s) of the low‐S samples remains unidentified; one compositionally resembles “gold‐anchor period” (phosphatic) Chelsea porcelain (London, ca. 1756–1769) but its decoration is inconsistent with known wares produced by this factory during that era. The degree of vitrification is highly variable, particularly among the SO₃‐poor samples. The melt phase is strongly enriched in incompatible elements (Ti, Fe, Na, K). The phosphate phase [calcined bone ash (hydroxyapatite)] in poorly vitrified samples hosts minute melt blebs, but remains porous. With increasing vitrification, these melt blebs increase in size and begin to coalesce, ultimately forming ameboid patches up to ∼10 μm in diameter. In the most vitrified samples, the coalesced melt “leaks” into the matrix, leaving behind a phosphate phase that lacks pores and melt and has a lower CaO/P₂O₅ ratio (=2.7, molecular proportions) than either hydroxyapatite (3.3) or β‐whitlockite (3.0). The two varieties of phosphate occur in some poorly vitrified samples, suggesting the recycling of high‐fired wasters (as “grog”) in their ceramic pastes. Melt compositions vary with contiguous mineralogy, accounting for their divergence from the ternary eutectic in the Ca₃(PO₄)₂‐CaAl₂Si₂O₈‐SiO₂ system. The resorption of phosphate by the matrix melt virtually precludes recognition of anorthite formed by the “non‐phosphate glass equation.” © 2011 Wiley Periodicals, Inc.     

Mineralogical and Geochemical Constraints on the Sediment Sources of Late Stone Age Pottery from the Birimi Site,Northern Ghana

The mineralogy and bulk chemical compositions of 15 Kintampo (Late Stone Age) potsherds from the Birimi site on the Gambaga Escarpment and eight samples of local sediment were determined with the intent of characterizing these wares and identifying the material used in their manufacture. Sediment from clay pits still used by potters north of the escarpment contains iron‐rich laterite clasts (100 × XFeO_t = 100 × FeO_t/[FeO_t + Al₂O₃ + SiO₂] ≥10). Sedimentary clasts in stream sediments are relatively siliceous and iron‐poor (100 × XFeO_t < 10). Bulk geochemical data together with the compositions of lithic clasts (laterite, siltstone/sandstone) link the pottery to sediment sources, including escarpment sediments not presently used by Ghanaian potters. Fresh granite clasts found in some of the sherds were not found in the analyzed sediment samples, although some of their distinctive mineralogical constituents (e.g., variably barian alkali feldspar) are present. The analytical data suggest that pots found at Birimi were made locally by mixing escarpment sediment with clay and stream sediment brought in from below the escarpment. This contrasts with present‐day practice, whereby the pots themselves are imported. The place where Birimi pottery was made and the outcrop source of aluminous sediment (mudstone with an “escarpment” trace element signature) used in these wares, however, remain unidentified. © 2013 Wiley Periodicals, Inc.     

Synthesis of cordierite using industrial waste fly ash

Fly ash is a product arising from coal combustion in thermal power plants. It represents a major source of environmental pollution. It is well known by its chemical composition rich of SiO₂ and Al₂O₃. With the aim of preserving the environment against this contamination, fly ash was used along with the starting materials for producing glass cordierite (2MgO, 2Al₂O₃, 5SiO₂). Four formulations were developed by mixing the silica gel, magnesium chloride (MgCl₂.6H₂O) and fly ash in the percentages enclosing the stoichiometry of cordierite (2MgO, 2Al₂O₃, 5SiO₂). Different experimental techniques (DTA/TGA, X-ray diffraction, FTIR and SEM) were used to characterise the prepared formulations. The results shown that for all formulations, a cordierite phase was obtained at 1200 °C along with several secondary phases such as mullite, cristobalite, silicon oxide, enstatite and spinel. At 1300 °C, pure indialite (α-cordierite) was obtained along with a small amount of spinel. The four formulations sintered at 1200 °C exhibit a homogenous morphology and high porosity. The acicular-shaped indialite grains were observed in both formulations with excess of alumina and excess of magnesia.     

Geology and Hydrothermal Alteration of the Milyang Pyrophyllite Deposit, Southeast Korea

Abstract: The Milyang pyrophyllite deposit, which is embedded in the Late Cretaceous Yuchon Group of the Kyongsang Supergroup, is one of the largest hydrothermal clay deposits in the Kyongsang basin, southeast Korea. Host rocks of the deposit are porphyritic andesite lava and minor andesitic lapilli tuff. In the Milyang district, a hydrothermally altered zone is about 2 × 3 km in extent; we can recognize the concentric arrangement of advanced argillic, propylitic, and sericitic alteration zones from the central to peripheral parts of the zone. The Milyang pyrophyllite deposit forms a part of the advanced argillic alteration zone. The Milyang pyrophyllite deposit is subdivided into the following four zones based on mineral assemblages: the pyrophyllite zones 1, 2, 3, and the silicified zone. The pyrophyllite zone 1, which occupies the central part of the deposit, comprises mainly pyrophyllite, kaolinite, and diaspore without quartz. Diaspore nodules often concentrate in beds 40–50 cm thick. Andalusite, dumortierite, and tourmaline locally occur as network veins, crack‐filler, or small spherulitic spots. The Al₂O₃ content of the ore ranges from 27 to 36 wt%. The pyrophyllite zone 2, which constitutes a major part of the deposit, comprises mainly pyrophyllite, kaolinite, and quartz. The Al₂O₃ content of the ore ranges from 15 to 24 wt%. The pyro‐phyllite zone 3 is the hematite‐rich marginal facies of the deposit. The silicified zone, which occurs as beds and septa, is mostly composed of quartz with minor pyrophyllite and kaolinite; the SiO₂ contents range from 79 to 90 wt%. Comparing chemical compositions of the high‐Al ores with those of unaltered host andesite, the Fe, Ca, alkalis, HFSE, and HREE contents are significantly depleted, whereas S, B, As, Sr, and LREE are enriched. The hydrothermal alteration of the Milyang pyrophyllite deposit can be classified into the following four stages: 1) extensive sericitic and propylitic alteration, 2) medium‐temperature (200–250°C) advanced argillic alteration, 3) high‐temperature (250–350°C or more) advanced argillic alteration, and 4) retrograde low‐temperature alteration. The heat and some volatile components such as B and S would be derived from the Pulguksa Granite intruded underneath the deposit.     

New constraints on granulite facies metamorphism and melt production in the Lewisian Complex,northwest Scotland

In this study, we investigate the metamorphic history of the Assynt and Gruinard blocks of the Archean Lewisian Complex, northwest Scotland, which are considered by some to represent discrete crustal terranes. For samples of mafic and intermediate rocks, phase diagrams were constructed in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ (NCKFMASHTO) system using whole‐rock compositions. Our results indicate that all samples equilibrated at similar peak metamorphic conditions of ~8–10 kbar and ~900–1,000°C, consistent with field evidence for in situ partial melting and the classic interpretation of the central region of the Lewisian Complex as representing a single crustal block. Melt‐reintegration modelling was employed in order to estimate probable protolith compositions. Phase equilibria calculated for these modelled undepleted precursors match well with those determined for a subsolidus amphibolite from Gairloch in the southern region of the Lewisian Complex. Both subsolidus lithologies exhibit similar phase relations and potential melt fertility, with both expected to produce orthopyroxene‐bearing hornblende granulites, with or without garnet, at the conditions inferred for the Badcallian metamorphic peak. For fully hydrated protoliths, prograde melting is predicted to first occur at ~620°C and ~9.5 kbar, with up to 45% partial melt predicted to form at peak conditions in a closed‐system environment. Partial melts calculated for both compositions between 610 and 1,050°C are mostly trondhjemitic. Although the melt‐reintegrated granulite is predicted to produce more potassic (granitic) melts at ~700–900°C, the modelled melts are consistent with the measured compositions of felsic sheets from the central region Lewisian Complex.