To understand the genetic relationship between hisingerite material in the joints of an overlying grey basalt and nontronite and Fe-rich saponite in the joints and matrix of a more deuterically altered, underlying green basalt, the hisingerite material was treated in a series of hydrothermal experiments. No well-ordered clay mineral was produced at temperatures <340°C, although extended treatment for 445 days and at 110°C or 42 days at 180°C resulted in the formation of materials that gave broad, weak, basal X-ray powder diffraction (XRD) reflections characteristic of 2:1 phyllosilicates. Hematite did not form at 110°C, but it did form at 180°C in 1- and 6-week runs. Treatments at 340°C in Pt, Ag-Pd, and Au containers resulted in mixtures of Fe-rich saponite + hematite, but the same starting material treated at 340°C in stainless steel yielded, in addition, some chlorite, probably due to the more reducing conditions in the stainless steel container. Treatment of the unaltered grey basalt at 340°C and 50 MPa for 10 days resulted in complete alteration of olivine (and probably glass) to a trioctahedral smectite.

The Fe-rich saponite produced by the hydrothermal treatment of the hisingerite material has a composition and XRD pattern similar to the Fe-rich saponite found in the green basalt and an XRD pattern similar to that produced by the hydrothermal treatment of the grey basalt; thus these clays may have had a similar origin. The compositions and XRD patterns of these clays are not similar, however, to those of the nontronite in the joints of the green basalt. The nontronite probably formed during a subsequent low-temperature alteration.

Solutions containing AlCl3 and Si(OH)4 (concentrations ≤ 1.5 mM with molar Si:Al ratios of 1:2, 1:1 and 3:1) and FeCl2 (0, 0.5 and 1.0 mM) were adjusted to pH 8 with Ca(OH)2, and incubated at 23°C and 89°C without exclusion of air in the presence of CaCO3 for 8–12 weeks. The products were characterized by infrared spectroscopy and X-ray diffraction. Systems with 3:1 and 1:1 Si:Al ratios without Fe gave hydrous feldspathoids at 23° and 89°C. Systems with 3:1 Si:Al ratios containing Fe gave aluminous nontronites at 89°C and noncrystalline, nontronite-like products at 23°C. Systems with 1:1 Si:Al ratios with added Fe gave Fe(III)-substituted hydrous feldspathoids at 23°C. At 89°C, the system with 1:1 Si:Al ratios and 0.5 mM Fe produced a “protohalloysite,” while that with 1.0 mM Fe gave a poorly ordered nontronite-like layer silicate. In systems with 1:2 Si:Al ratios, the formation of “protoimogolite” at 23°C was little affected by additions of Fe. At 89°C, the “protoimogolite” decomposed to boehmite and poorly-ordered layer silicate phases. Inclusion of 1 mM MgCl2 in the above systems had no effect on the products at 23°C, but at 89°C produced saponites and a mixed layer saponite-chlorite in the 3:1 Si:Al systems, and saponite-like layer structures in the 1:1 and 1:2 Si:Al systems.

A material resembling what has been described in the literature as hisingerite has been identified in the joints of Cenozoic grey basalt near Geelong, Victoria. The material gives an X-ray powder diffraction pattern with weak broad peaks at 4.49, 2.58, and 1.53 Å and a chemical analysis of SiO2 = 34.2, TiO2 = 0.28, A12O3 = 4.16, Fe2O3 = 17.10, FeO = 3.52, MnO = 0.04, MgO = 5.19, CaO = 0.68, Na2O = 0.26, P2O5 = 0.05, H2O+ = 5.3, H2O− = 25.4, total = 96.18% (3.82% siderite impurity). Assuming a smectite model with 44 negative charges per unit cell, the chemical composition gives a unit-cell formula with −1.14 charges, corresponding to a cation-exchange capacity (CEC) of 135 meq/100 g. The same unit-cell charge is obtained when the structural formula is calculated on the basis of (Si + Al) = 8. The measured CEC of 60 meq/100 g indicates that the smectite structure may not apply to this hisingerite-material, and that in the alternative structure, all of the Al atoms may not be in the tetrahedral positions. Although the specific surface area of this material is between 662 and 758 m2/g (comparable to that of smectite), the infrared spectra do not show the characteristic OH vibrations, and the thermal analysis curves lack the dehydroxylation peak at 550–600°C expected for a smectite. Transmission electron microscopy shows indications of a layer structure and apparently hollow spherical bodies with ‘onion’ structure of 140 to 200 Å internal diameter, which might represent the sites of the large amounts of water contained by the material. The mode of occurrence and the nature of the hisingerite-material suggest precipitation from solution at relatively low temperatures.

The crystal chemistry of Fe-Si scales deposited from geothermal brines at Salton Sea, California, was studied by powder X-ray diffraction and spectroscopic techniques including infrared, 57Fe Mössbauer, 27Al and 29Si nuclear magnetic resonance (NMR), and Fe and Si K-edge extended X-ray absorption fine structure (EXAFS). Scales precipitated at near 250°C from dissolved ferrous iron and silicic acid are composed of hisingerite. This phase is shown to possess the same local structure as nontronite and is a poorly-crystallized precursor of the ferric smectite. A clear distinction can be made at the local scale between hisingerite and 2-line ferrihydrite because, even in their most disordered states, the former possesses a two-dimensional and the latter a three-dimensional anionic framework. At temperature near 100°C Fe-Si scales are a mix of Al-containing opal and hydrous ferrous silicate, whose local structure resembles minnesotaite and greenalite. This hydrous ferrous silicate is very well ordered at the local scale with an average Fe coordination about Fe atoms of 6 ± 1. The difference in crystallinity between the ferrous and ferric silicate scales was related to variations of growth rates of clay particles precipitated from ferrous and ferric salt solutions. The low crystallinity of the ferric smectite suggests that the oxidation of ferrous iron occurs before polymerization with silica.

Hisingerite, first described in 1810, has been variously regarded as noncrystalline, as a septechlorite, as ferric allophane, as ferric halloysite and as poorly crystalline nontronite. Hisingerite from the original localities of Gillinge and Riddarhyttan in Sweden has a composition close to Fe2O3·2SiO22H2O. X-ray diffraction (XRD) analysis of Riddarhyttan hisingerite yields very broad maxima at 7.7, 4.44, 3.57, 2.56, 2.26, 1.69 and 1.54 Å, and that from Gillinge is similar. Cation exchange capacities are 2.2 meq/100 g (Riddarhyttan) and zero (Gillinge). Transmission electron microscopy (TEM) shows a fabric of concentric spheres and part spheres, with diameters of about 140 Å and walls up to six 7-Å layers thick. High-resolution images of the sphere walls reveal a 2-layer structure similar to that of kaolinite. A calculated diffraction pattern based on a model of 4 concentric shells of ferric kaolinite structure matches the observed pattern quite closely. Some other hisingerites, notably that from Bellevue King Mine, Idaho, show 10-Å layers as well as 7-Å layers, and this hisingerite has a CEC of 32 meq/100 g and a weak 15.5-Å X-ray reflection in addition to a pattern similar to Riddarhyttan hisingerite. It is concluded that hisingerite is a curved ferric 7-Å 1:1 layer silicate analogous to halloysite, and that many of the hisingerites reported in the literature contain admixed nontronite.

Weathering of chlorite adjacent to macro- and micro-passages (fissures) in regolith units has been studied to determine the alteration mechanisms and products and compare them to those that prevail at a distance from the open passages. The micro-fissures in the saprolith units evolve as a function of weathering with an increase in micro-fissure density and their infilling with ferriargillans corresponding to an increase in weathering intensity. In the saprock and saprolite units, goethite-rich bands with surrounding reddish haloes invade the chlorite adjoining the micro-fissures. In the reddish haloes surrounding the goethite bands and fissures, the phyllosilicates alter to an intimate mixture of goethite, kaolinite, feroxyhyte and halloysite with the possible nanoscale presence of other fine-grained iron aluminosilicates such as hisingerite and smectite. In the fine saprolite, the weathering products after original chlorite adjoining the micro-fissures bearing ferriargillans, alter directly to ferriargillan products — kaolinite and goethite. The lack of orientation of the products with the parent phyllosilicates indicates the operation of a dissolution-precipitat ion mechanism which is in contrast to the topotactic alteration mechanism functioning at a distance within the phyllosilicate grain assemblage. The differences in alteration mechanisms and products of chlorite weathering in different microsites suggest the rate of weathering of chlorite can differ in microsites within individual regolith units. The presence of fine-grained metastable products in the form of feroxyhyte and halloysite adjoining the fissures suggests an Ostwald Step Rule sequence during alteration of phyllosilicates with rapid oxidation of Fe and the presence of Si in the microsite considered the main factor favoring fine-grained metastable products.