605 m of sediments were cored in Hole 841 of the Ocean Drilling Program (ODP) at the Tonga Trench margin. The sedimentary sequence consists mainly of Miocene vitric siltstones, vitric sandstones, and volcanic conglomerates. A major consideration for selecting this site was the presence of abundant authigenic minerals (40% to 70% of the whole rock), which consist of K-feldspars, clays, thaumasite (Ca3Si(OH)6CO3SO4, 12H2O), and zeolites. The zeolite minerals include phillipsite, clinoptilolite, analcime, mordenite, chabazite, heulandite, wairakite, and erionite. The increasing amount of analcime from 257 mbsf to 470 mbsf, and the joint occurrence of mordenite and wairakite in this zone of Miocene tufts, seems to be induced by the heat flow from a major intrusive sequence of basaltic andesite sills and dikes. This abundance of analcime in response to the thermal pulse could explain the unusual Na-depleted porewater compositions observed in ODP Hole 841.

The terms “hydrophobic” and “hydrophilic” are typically used in a non-specific sense and, as such, they have a limited utility. Surface thermodynamic theory, as described here, allows a natural and potentially powerful definition of these terms. The boundary between hydrophobicity and hydrophilicity occurs when the difference between the apolar attraction and the polar repulsion between molecules or particles of material (1) immersed in water (w) is equal to the cohesive polar attraction between the water molecules. Under these conditions, the interfacial free energy of interaction between particles of 1, immersed in water (ignoring electrostatic interactions), exactly zero. When is positive, the interaction of the material with water dominates and the surface of the material is hydrophilic; when is negative, the polar cohesive attraction between the water molecules dominates and the material is hydrophobic. Thus, the sign of defines the nature of the surface and the magnitude of may be used as the natural quantitative measure of the surface hydrophobicity or hydrophilicity.

The Middle Proterozoic (1.1 Ga) Nonesuch Formation, host of the stratiform copper deposit at White Pine, Michigan, consists of 200 m of principally dark grey clastic sediments which contain detritus obtained dominantly from underlying mafic to intermediate volcanic rocks. Clay minerals from samples collected from the mine area and drill holes up to 100 km away have been studied using SEM, EMPA, TEM and AEM. Two morphologies of phyllosilicates, both including white mica and chlorite, occur in the ‘lower’ Nonesuch Formation: (1) detrital-shaped and (2) matrix. Detrital-shaped phyllosilicate grains are up to 450 microns long with long axes parallel to bedding. Matrix phyllosilicates occur as packets typically <200 Å thick and as pore-filling cement.

TEM images of detrital-shaped chlorite generally display 14-Å periodicity, although 24-Å corrensite- like units occur locally. Most detrital-shaped chlorite from the mine area samples have a relatively restricted range of Fe/(Mg+Fe) ratios from 0.52 to 0.58, but the Fe/(Fe+Mg) ratios of detrital-shaped chlorite outside the mine area range from 0.27 to 0.64. TiO2 crystals occur within and surrounding the detrital-shaped chlorite. Matrix chlorite has Fe/(Fe+Mg) ratios of 0.47 to 0.63, indicating that it is relatively homogeneous and enriched in Fe compared to detrital-shaped chlorite.

Detrital-shaped white mica occurs as a 2Mi polytype and generally has a phengitic composition. Matrix illite-rich I/S occurs as a 1Md polytype, is K and Al deficient relative to end-member muscovite and contains significant Fe and Mg.

The data are consistent with homogenization of detrital-shaped chlorite in the White Pine mine area by hydrothermal fluids during copper mineralization. The TiO2 crystals and corrensite-like units in detrital- shaped chlorite imply that it is at least in part derived from alteration of biotite. The presence of immature 1Md illite-rich I/S and a one layer chlorite polytype with stacking disorder suggests that the matrix clays are in their original, post-smectite state of formation as consistent with an authigenic origin during early burial diagenesis; i.e., they have not undergone subsequent transformation even though sedimentation and ore deposition occurred prior to 1 Ga.

Estimations of the external specific surface areas (S.S.A.) by the N2-BET method of clay separates that were further fractionated by the high gradient magnetic separation technique revealed that the magnetic fractions had consistently lower S.S.A. compared to non-magnetic fractions. This phenomenon has been attributed, in the past, to the intimate association of Fe-oxides with silicate clays. It is the contention of this study that this reasoning is insufficient due to the following reasons. X-ray diffractograms (XRD) confirmed that heavy minerals were abundant in the magnetic fractions of these clays. Total chemical analyses and energy dispersive X-ray analyses showed that these heavy minerals contained Fe and Ti, which were not completely extracted by the dithionite-citrate bicarbonate (DCB) treatments. Crystallinity and quantity of these oxides in the different fractions did not show any relationships with the S.S.A. Lower S.S.A. were found in the magnetic fractions of both coarse and fine clays in the untreated as well as DCB-treated samples. The average particle density of the magnetic fractions was found to be higher than the non-magnetic fractions, resulting in an underestimation of the S.S.A. This underestimation was further proven when clay-sized illmenite (density = 4.79 Mg m−3) was found to have lower S.S.A. than quartz (density = 2.65 Mg m−3) and well-crystallized Georgia kaolinite (density = 2.61 Mg m−3), even though the illmenite particles were smaller in size compared to the kaolinite particles and similar in size compared to the quartz particles. It is, therefore, proposed that the specific surface areas should be expressed either on a volumetric basis or corrected for differences in density to avoid underestimations when heavy minerals are present in the samples.

The form under which Ti occurs in kaolinitic materials from various environments has been investigated using second derivative diffuse reflectance spectroscopy. The position of the absorption edge may be used as a diagnostic band to determine Ti-phases (anatase, rutile, Ti-gels). Ti-oxides may be detected in kaolins, down to 0.1 wt. % TiO2. Diffuse reflectance spectra show the presence of Ti-gel-like phases occluded in sedimentary kaolinite particles. These phases, which record conditions at the time of kaolinite growth, constitute the first direct evidence of Ti mobility at the scale of mineral assemblages and question the substitution of Ti for Al in kaolinite. The nature of the Ti-oxides associated with kaolinite particles gives some constraints on the temperature conditions of hydrothermal kaolins, the evolution of sedimentary kaolin during basin diagenesis and the source of parental material in soil kaolins.

SiO2 sols were made unstable by addition of Ca2+ ions. The resulting states of instability were classified as gelation, flocculation, and precipitation by means of observation, by checking the Tyndall effects on the supernatant or suspending solution, as appropriate, and by measuring the apparent densities of flocculated mass. The concentrations of free Ca2+ ions left in solution were measured by means of a Ca2+ ion selective electrode. The amounts sorbed onto SiO2 particles were then calculated by material balance. It was found that while the amount sorbed dictates the limit of stability, the SiO2 concentration in the mixture is an important factor deciding the state of instability. Depending on the SiO2 concentration, there were two distinct flocs with the apparent floc density of 6 ± 1 and 12 ± 1 mg SiO2/ml.

Single-crystal, X-ray examination of Mg,Fe-rich chlorites that were heated at 650°C for 24 hours in air and have undergone dehydroxylation of the interlayer shows that two product phases result with a topotactic relationship, with the c axis of both phases parallel. One phase (“modified chlorite” or “14-A phase”) has relatively sharp reflections with a 14-A c-axis repeat, indicating that it is well crystallized and maintains the 2:1 layer from the parent. Cell parameters are a = 5.368(1)A, b = 9.297(2)A, c = 14.215(6)A, a = 89.86(3)°, ß = 97.15(3)°, γ = 89.98(2)°, and it crystallizes in CĪ symmetry. A structure refinement, details of which will be reported later, indicates that the interlayer consists of two planes, each containing (M + O), where M is the interlayer cation species. These planes show about ±0.5A positional disorder along the [001] direction. There is no evidence for scattering material at z = 0.5 between the 2:1 layers. The second phase in the topotactic relationship is based on a 27-A unit c axis (“27-A phase”). The diffraction data are limited with about 15 diffuse reflections observed, indicating that it is poorly crystallized. The 27-A spacing suggests that both octahedral sheets in the parent chlorite contribute to the formation of this phase.

Heating Mg,Fe-rich chlorite powder in a closed system to 550°C, under either reducing or oxidizing conditions, prevents the formation of the 27-A phase. Because the 27-A phase forms in an open system, we infer that water fugacity is an important factor in its formation. Heating experiments involving samples with different polytypes and octahedral “type” (dioctahedral vs trioctahedral) of the 2:1 layer suggests that these two variables are important. However, the results are equivocal, and an ill-defined B-rich chlorite from Madagascar breaks the observed trends for both variations in stacking sequence and octahedral type. However, B-content may be a factor in the transformation also for those chlorites that contain B.

OH-Cr smectites were prepared with different mmol Cr/g smectite: 0.5, 1.5, 3.5, 5, 10 and 20 by treatment with hydroxy-chromium solution prepared at 60°C and one day of hydrolysis with OH/Cr = 2. The samples were characterized by X-ray diffraction (XRD), differential thermal analyses (DTA) and N2 adsorption-desorption isotherms.

The d(001) spacings of OH-Cr-smectite were different according to Cr added/g smectite. Larger d(001) spacings: 1.95, 2.05 and 2.07 nm were obtained with 5, 10 and 20 mmol Cr per gram of sample. DTA diagrams of smectite treated with OH-Cr solution showed exothermic peak at 420°C corresponding to Cr203 (confirmed by XRD). N2 adsorption-desorption isotherms of smectite treated with different amounts of Cr preserved the same slit-shaped pores than original sample, but with different micropore volume. This behavior was maintained until treatment temperature of 380°C. The specific area of smectite was increased from 36 to 175 m2/g after treatment with OH-Cr solution. The textural characteristics of OH- Cr smectite heated up to 420°C were changed. The specific area decreased and mesopore volume was produced. The different Cr added modified the structural and textural behavior.

Using theoretical profiles of diffracted X-ray intensity for interstratification between layers having d-spacings around 14.3 Å and 10.1 Å, a series of diagrams was derived from which the proportion of 14.3 Å layers (W14) and the probability of passing from a 14.3 Å layer to a 10.1 Å layer (P14/10) can be derived. W14 can be derived independently of P14/10 using the angular distance between reflections situated at 18.2° and 25.4° 2θ (CuKα). Once W14 is determined, P14/10 may be obtained using the angular width of the diffuse reflections between 27° and 34° 2θ. In this case, two different diagrams are proposed for P14/10 determination because experimental X-ray patterns show either one or two diffuse reflections. Comparison of five experimental patterns with theoretical patterns calculated using W14 and P14/10 obtained using these diagrams indicates that the method can be useful for determining W14 and P14/10 in unknown samples. Moreover, the method described is independent of the Lorentz polarization factor and the layer type. The d-spacings associated with the two kinds of layers, however, should be similar (± 1%) to those for which the determinative diagrams were calculated.

Redox cycles are common in nature and likely have a profound effect on the behavior of soils and sediments. This study examined a key component of redox cycles in smectites, namely, the reoxidation process, which has received little attention compared to the reduction process. Unaltered (oxidized) and reoxidized ferruginous smectites (nontronites) were compared using infrared and Mössbauer spectroscopies, and thermal gravimetric analysis. The infrared and thermal gravimetric data revealed that the structural OH content of reduced-reoxidized clay is about 15 to 20% less than in the original (oxidized) sample, indicating that the structure remains partially dehydroxylated even after reoxidation. Mössbaner spectra of reoxidized samples consisted of larger quadrupole splitting for Fe(III) doublets than in the unaltered samples, suggesting that the environment of Fe(III) is more distorted after the reduction-reoxidation treatment.

The corrensite from a chlorite vein-like rodingite blackwall in serpentinites has been studied. The proper identification of swelling layers in corrensite using heating at 500°C was ambiguous because of the spontaneous rehydration. Even K+-saturated samples heated to 500°C readily rehydrated after being cooled. This can be prevented if XRD patterns are recorded at 300°C, without cooling the sample. A standard heating at 500°C can result in partial decomposition of brucite-like sheet as evidenced by ASN simulation.

The ASN-calculated XRD patterns of contracted corrensite proved that an inhomogeneous distribution of heavy atoms (Fe, Ni, Mn, Cr etc.) between brucite-like sheet and talc-like layers and between two adjacent corrensite units in the interstratified mineral may result in the disappearance of low angle reflections (24 Å and 12 Å), which can lead to miscellaneous interpretation if distribution of heavy cations is not checked.

The corrensite occurred together with regular chlorite. However, it is assumed to be formed due to direct crystallization from late hydrothermal solutions as deduced from comparison of the Mg/(Mg + Fe) ratio in the corrensite, serpentinite and chlorite.

To obtain Cu-kaolinites with a controlled range of chemical compositions, syntheses were performed by hydrothermally ageing gels with kaolinite stoichiometric compositions. Gels were prepared with sodium metasilicate and nitrates of octahedral cations. Temperature of synthesis was 250°C with a corresponding equilibrium water pressure of 38 bars.

Three samples with copper contents ranging from 0.1 to 7% and another one with the chemical composition of the Cu end-member were synthesized. While this fourth sample led to tenorite after the hydrothermal treatment, the three others crystallized well into kaolinite.

Up to almost 1% CuO was measured by TEM in some isolated ‘clean’ and hexagonal kaolinite particles. EPR and XPS spectroscopies were consistent with an octahedral position of Cu2+. In IR spectra, vAl-OH-Cu absorption bands were not observed, but vAl2OH bands appeared more and more blurred when Cu content of samples increased. Weak bands situated at 868 cm−1 and 840 cm−1 are tentatively attributed to δAlCuOH. By differential thermal analysis, a downward shift of 20°C in temperature of the endothermic peak from the less Cu-rich sample to the most Cu-rich one, argued for the existence of some Al-OH-Cu bonds, whose binding energies are presumed to be less than the Al-OH-Al ones.

In view of these results, Cu2+ appears incorporated in the octahedral sheet of kaolinite. Moreover, this incorporation is made without major perturbation of the kaolinite structure.

The influence of different ions in the formation of Al(OH)3 polymorphs has been studied experimentally by promoting stoichiometric reactions between the aluminum salts (AlCl3, Al(NO3)3, Al2(SO4)3) and bases (NaOH, KOH, NH4OH). In all cases the polymorphs obtained were a mixture of gibbsite, bayerite and nordstrandite or pseudoboehmite with the exception of the reaction between KOH, or NH4OH and Al2(SO4)3 which produced amorphous gels. Ageing of these gels at ambient temperature and pressure for 180 days or at 60°C for 20 days resulted in crystalline structure. Specifically, pseudoboehmite was crystallized from the reaction between Al2(SO4)3 and NH4OH. Significantly, of all ions present in solution in the present experiment, only the sulphate ones were observed to have a marked influence in the precipitation of Al oxyhydroxides.

The hot spring water discharging from a flank of an active volcano is precipitating unique monomineralic manganese deposits over volcanic terrain. The major and trace element chemistry, XRD mineralogy, DTA, and SEM observations indicate that the deposits consist of 10 Å phyllomanganate (buserite) accommodating inter-layer Ca and Mg with negligible amounts of detrital minerals. Other metallic elements can be accommodated by buserite, but concentrations are negligible ranging less than 10 ppm to 500 ppm. Abundance and pattern of REE (less than 100 ppm in total) are similar to those from hydrothermal manganese deposits. The buserite is enriched in Ca and Mg but depleted in Na in comparison with those in the spring water. The distribution coefficients for Ca, Mg and Na between the buserite and the host water were calculated assuming an ion-exchange equilibrium in the Yuno-Taki Fails, which proved applicable to other manganese deposits from surficial environments on land and oceans.