Clay swelling, an important phenomenon in natural systems, can dramatically affect the properties of soils and sediments. Of particular interest in low-salinity, saturated systems are osmotic hydrates, forms of smectite in which the layer separation greatly exceeds the thickness of a single smectite layer due to the intercalation of water. In situ X-ray diffraction (XRD) studies have shown a strong link between ionic strength and average interlayer spacing in osmotic hydrates but also indicate the presence of structural disorder that has not been fully described. In the present study the structural state of expanded smectite in sodium chloride solutions was investigated by combining very low electron dose, high-resolution cryogenic-transmission electron microscopy observations with XRD experiments. Wyoming smectite (SWy-2) was embedded in vitreous ice to evaluate clay structure in aqua. Lattice-fringe images showed that smectite equilibrated in aqueous, low-ionic-strength solutions, exists as individual smectite layers, osmotic hydrates composed of parallel layers, as well as disordered layer conformations. No evidence was found here for edge-to-sheet attractions, but significant variability in interlayer spacing was observed. Whether this variation could be explained by a dependence of the magnitude of long-range cohesive (van der Waals) forces on the number of layers in a smectite particle was investigated here. Calculations of the Hamaker constant for layer-layer interactions showed that van der Waals forces may span at least five layers plus the intervening water and confirmed that forces vary with layer number. Drying of the disordered osmotic hydrates induced re-aggregation of the smectite to form particles that exhibited coherent scattering domains. Clay disaggregation and restacking may be considered as an example of oriented attachment, with the unusual distinction that it may be cycled repeatedly by changing solution conditions.

The new mineral anorpiment, As2S3, the triclinic dimorph of orpiment, has space group PI and cell parameters a = 5.7577(2), b = 8.7169(3), c = 10.2682(7) Å, α = 78.152(7), β = 75.817(7), γ = 89.861(6)°, V = 488.38(4) Å3 and Z = 4. It occurs at the Palomo mine, Castrovirreyna Province. Huancavelica Department, Peru. It is a low-temperature hydrothermal mineral associated with dufrenoysite, muscovite, orpiment, pyrite and realgar. It occurs in drusy crusts of wedge-shaped, transparent, greenish yellow crystals. The streak is yellow. The lustre is resinous on crystal faces, but pearly on cleavage surfaces. The Mohs hardness is about VA. The mineral is sectile with an irregular fracture and one perfect and easy cleavage on ﹛001﹜. The measured and calculated densities are 3.33 and 3.321 g cm–3, respectively. All indices of refraction are greater than 2. The mineral is optically biaxial (—) with 2V = 35—40° and no observed dispersion. The acute bisectrix (X) is approximately perpendicular to the ﹛001﹜ cleavage. Electron microprobe analyses yielded the averages and ranges in wt.%: As 58.21 (57.74–59.03), S 38.72 (38.33–39.00), total 96.94 (96.07–97.75), providing the empirical formula (based on 5 atoms) As1.96S3.04. The strongest powder X-ray diffraction lines are [d (hkl) I] 4.867(002) 97, 4.519 (110,11̄1) 77, 3.702 (1̄1̄1) 46, 3.609 (022,11̄2) 82, 2.880(201,02̄2,1̄2̄1,023) 75, 2.552 (1̄13,1̄31,132) 100, 2.469 (114,130,13̄1) 96. The structure of anorpiment [R1 = 0.021 for 1484 reflections with F0 > 4σ(F)] consists of layers of covalently bonded As and S atoms. Each S atom bonds to two As atoms at As—S—As angles between 100.45 and 104.15°. Each As atom is strongly bonded to three S atoms at S—As—S angles between 91.28 and 103.59°, forming an AsS3 pyramid with As at its apex. The As—S linkages within the layers form rings of six AsS3 pyramids. Interlayer bonding forces are interpreted as van der Waals. The structure of anorpiment is similar to that of orpiment in that it is composed of layers of As2S3 macromolecules, but arranged in a different stacking sequence.