The Smithsonian Institution Building, commonly referred to as the Castle, is located on the National Mall in Washington, DC, and was constructed in the mid-nineteenth century for the purpose of housing all museum and scientific functions for the newly formed institution. Matching gateposts designed by the Castle's architect were erected more than a century later in the Enid A. Haupt Garden opposite the Castle. Black patches were recently noted on both structures, which are clad with locally quarried Seneca red sandstone. Portable x-ray fluorescence (XRF) spectrometry links the discoloration with elevated Mn concentrations. The discolored patches resemble rock varnish, a Mn-rich coating observed on rock surfaces formed in a variety of environments. Bulk rock and varnish chemistry, in addition to microscopy and microanalysis of the varnish, are presented here. On a bulk chemical basis, the Seneca sandstone is relatively poor in Mn, containing ~500 ppmw. In contrast, the rock varnish is greatly enriched in Mn relative to the stone and to a lesser degree in Pb, Ca, Zn, Cu and Ni. Cross sections of the black encrusted regions show that the stone's red coloration has been modified by black pigmentation from the surface down to ~250 μm. X-ray diffraction of blackened particles produced no discernable pattern, indicating concentrations below the detection limit, poor crystallinity, or both. Scanning electron microscopy and EDS-based x-ray microanalysis of the uppermost portion of the cross section reveal nanometer scale (<20-200 nm) Mn-rich and clay particles concentrated in a thin film (≪1 μm) at the surface. Additionally, Mn oxide particles decorate the surfaces of fine-grained minerals in sandstone pores within the discolored zone. Imaging and microanalysis of the rock surface reveal that the Mn-rich varnish is a discontinuous film ≪1 μm in thickness with an estimated composition of Na 0.2 Ca 0.1 Mg 0.1 Al 0.1 Si 0.5 Mn 1.9 Fe 0.5 O 6.7 . This composition most likely represents a nanoscale mixture of a Mn oxide (e.g., birnessite or todorokite) and an Al-rich silicate mineral. Seneca sandstone on the Smithsonian Castle and gateposts is discolored in patches owing to the Mnrich phase being deposited into two zones: (1) a vanishingly thin patina, and (2) nanoparticles coating grain boundaries and pores in the uppermost ~200-250 μm of the stone. While the mineralogy is similar to well-studied varnish formed in arid settings, rock varnish on the Smithsonian structures is significantly thinner. Because this architectural rock varnish is young, it may represent the earliest stages of formation of the more commonly described varnishes reported in the literature.
Three fragmentary faces originally plastered on skulls are discussed : their excavation history, conservation treatment, and technical analysis. Deposited during the Pre-pottery Neolithic В in a shallow pit at the site of 'Ain Ghazal, Jordan, the modelled faces had apparently been broken off the skulls. Only plaster was found, and the absence of the skulls enabled many aspects of manufacture to be determined during reassembly. Skulls without their mandibles had been prepared by stuffing cavities with grass and coiling rope below the maxillae. Results of plaster analysis using a range of scientific techniques are presented. Stylistic and technical comparisons are made to other Neolithic plastered skulls, as well as to large statues found at the site.
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