Two soil sequences in northern Italy (Val di Fiemme and Val Genova) along an elevational gradient ranging from moderate (950 m a.s.l.) to high alpine (2440 m a.s.l.) climate zones were investigated with respect to element losses (Ca, Mg, K, Na, Fe, Al, Si, Mn) and development of clay minerals. Soils formed on paleo-rhyolitic parent material in Val di Fiemme and on tonalitic-granodioritic morainic material in Val Genova. All the soils have a similar age (∼12,000 y) and have been classified as Podzols. The soils are very acid and the pH values tend to increase with decreasing altitude. Podzolization processes were most intense in the range of the subalpine forest up to the timberline (1400–1900 m above sea-level (a.s.l.)). Element leaching was greatest in this range and weathering rates decrease with both higher and lower altitudes. Due to the different lithologies and precipitations between the two valleys, the total amount of chemical weathering was slightly different, although the same trends with altitude could be observed. Imogolite-type materials (ITM) are generally of minor importance. Greater concentrations of ITM were observed in the Bhs or Bs horizons of the Episkeleti-Entic Podzols at the lower altitudes. Iron eluviation was similar in all Podzols while larger amounts of eluviated Al were detected in Val Genova. The pattern of smectite distribution along the climosequences had similarities to the trend of cation losses. The largest amount of low-charge expandable minerals seems to exist in the range of the subalpine forest up to the timberline. The development of clay minerals with a smaller layer charge was more advanced in Podzols on rhyolitic material where smectite could be detected in the Bhs and Bs horizon. Parent material influenced chemical weathering in the soils along the two climosequences and essentially determined the degree of weathering and the formation of clay minerals.

Apophyllite, a hydrous K-Ca-phyllosilicate, reacts with acidic aqueous solutions at room temperature. Various analytical methods have been applied to study the mechanism of the reaction and its characteristics, i.e. the changes in chemical composition, modifications in crystal structure and alterations in surface morphology. In contact with acidic solution, protonation of the terminal, non-bridging oxygen at the silicate tetrahedra takes place and the interlayer cations K+ and Ca2+ are removed. The protonation and ion removal causes the interlayer spacing to increase. Atomic force microscopy shows that the increase takes place discontinuously and, therefore, reflects a discontinuous reaction that comprises a two- or three-step protonation. Additionally, three structurally different protonation sites have been detected by nuclear magnetic resonance spectroscopy which also differ in the amount of close-by hydrogen, although in pristine apophyllite all terminal oxygen positions at silicate tetrahedra are structurally equivalent. In many clay minerals such structurally different protonation sites have not been detected so far. Thus, the multi-step protonation process in apophyllite clearly demonstrates the vast sensitivity of the protonation reaction on small structural variations in phyllosilicates.

The clay fraction of the sedimentary succession beneath the Mahakam Delta (eastern Kalimantan, Indonesia) consists mainly of mixed-layer illite-smectite, with minor amounts of kaolinite and/or dickite, discrete detrital illite and chlorite. On the near-shore anticline, evolution of this mixed-layer material is characterized by a decrease in expandability with depth. The mechanism of conversion of smectite to illite layers depends on the lithology of the host rocks: it evolves along a solid-state transformation in the shales and a dissolution-precipitation in the sandstones.

Illite fundamental particles from two sandstones buried at ∼4000 m in the Tambora field next to the Handil field on the same near-shore anticline yield a mean K-Ar age of 15.7±1.6 Ma (2σ), which is younger than the stratigraphic age but still slightly biased by minute amounts of discrete detrital illite. Recalculated after modeling, which takes into account the occurrence of the discrete detrital illite, this K-Ar age becomes 14.4±0.7 Ma. The K-Ar values of the fundamental particles from associated buried shales are significantly older, which can be explained by a mixture of (1) a precursor material similar to that presently deposited in the delta of the Mahakam River, and (2) authigenic fundamental particles incorporating Ar with a 40Ar/36Ar ratio above atmospheric value during nucleation and growth on the same detrital precursor.

Application of the modeling to the burial evolution of <0.4 µm particles from both the shales and the sandstones of the basin points to a contribution of detrital micaceous material in both lithologies, (1) in the sandstones as a detrital component dissolving progressively and mixed mechanically with the authigenic fundamental particles, and (2) in the shales as a detrital precursor progressively releasing radiogenic 40Ar by burial alteration, and at the same time acting as a support for the fundamental particles for the growth of authigenic fundamental particles that were found to incorporate Ar characterized by an excess of 40Ar.

Limited information is available on microporosity in soils. A study was undertaken to investigate the micropore characteristics of four soil samples, with different particle-size distributions, and four natural silicate clay minerals. Specific surface area and the differential micropore-size distribution were taken into account to characterize the microstructure of the soils and clays. The micropore-size distributions showed a maximum contribution to the total microporosity by pores having an effective pore radius of ∼20 Å, thus indicating that that category of pore contributes more than others to the total microporosity of the system. For both soils and clays a good exponential correlation was found between the maximum contribution to the microporosity and their specific surface area. A linear relationship was also found between the microporosity of the soils and their clay content. It has been concluded that the micropore system formed by 20 Å pores is mainly located in the clay fraction of the soil, and contributes significantly to defining some of the most notable physicochemical properties of soils and clays.

L-aspartic acid was intercalated into layered double hydroxides by coprecipitation. Two types of well crystallized material were obtained and were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry, differential thermal analysis and polarimetry. Schematic models of two intercalation structures with different basal spacings are given. It is proved that the optical activity of L-aspartic acid is retained during and after the intercalation process.

The Precambrian Villa Mónica Formation clay was analyzed using petrographic and scanning electron microscopy, X-ray diffraction and chemical analysis, with the aim of characterizing the Ti-bearing phases present and determining their possible origin and/or source. Two Ti-bearing minerals were found to be present, rutile and anatase. The crystals are needles between 5 and 15 µm in size, with no evidence of abrasion or corrosion. They are commonly found in association with the (001) faces of illite flakes or in the pores between the flakes. Their disposition is similar in the three quarries studied. No zonation or differential settling due to differences in specific gravity was observed. In addition, chemical analyses indicated a positive correlation between TiO2 and K2O suggesting that both oxides behave similarly after the deposition of the sediment. The TiO2 content in the bulk fraction ranges from 0.8 to 1.98 wt.%, values that are similar to those exhibited in other clay deposits from different ages and geneses.

All observations are consistent with an in situ origin of these Ti-bearing phases during post-depositional processes that included recrystallization of existing minerals and crystallization of new phases. The original detrital minerals such as biotite, ilmenite as well as detrital illite, were the primary sources of the TiO2 and of the Fe oxides that coat the clay. Understanding the origin and the reaction mechanisms involved during the post-depositional alteration of the Villa Mónica Formation suggests that the Ti-bearing phases in different sediment types were formed by similar mechanisms involving redox processes at low to medium temperatures, even in Precambrian sediments where the presence of rutile could lead to an incorrect assumption of high temperatures involved.

The polyphenol theory of humic-substance formation has been studied extensively; however, an alternative theory, that humic substances are formed through the condensation of amino acids and reducing sugars (Maillard reaction), has not been explored to the same extent. The general objectives of this study were to determine whether smectites and goethites catalyze the abiotic polymerization of arginine and glucose to form humic-like compounds. The effects of smectite type, saturating cation, and the degree of Al substitution in goethites on the polymerization reaction were also studied. Four cation-saturated smectites and four Al-substituted goethites were incubated abiotically with solutions containing a mixture of arginine + glucose for 21 days at 37°C. After the incubations, total C recovered ranged from 80.6 to 123.8% and from 100.5 to 105.1% for the smectite and goethite systems, respectively. At the end of the incubations, 21.4–50.3% of the added C and 16.5–90% of the added N were sorbed on the various smectites, and 6.2–9.0% of the added C and 2.3–4.6% of added N was sorbed on the goethites in a form that could not be desorbed by washing with 100 mM CaCl2. X-ray diffraction analysis indicated that some of the sorbed C was intercalated in the smectites and FTIR analysis provided evidence of new absorption bands at 1650 and 1668 cm−1, which are consistent with Maillard reaction products. Thus, it is concluded that smectites catalyze the condensation of arginine and glucose to form humic-like products. Goethites, however, have little or no ability to catalyze this reaction.

A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ∼0.99 mg/m2, which corresponds to ∼0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (∼725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

Silicic vitric tuffs of the Alaçatı (Çeşme) area, west of Izmir (Turkey), are partly altered to authigenic zeolites and clay minerals. Mordenite and clinoptilolite-heulandite accompanied by smectite are the main alteration products of the tuffs. Scanning electron microscope examination indicates that mordenite forms mainly from a gel-like precursor and to a lesser degree from volcanic glass. Mordenite and clinoptilolite-heulandite have formed by the hydrolysis and dissolution of silicic vitric tuffs by thermal waters which circulated through the fracture zone into porous vitric tuffs. These thermal waters, which resulted from mixing of thermal (Na-Cl type) and groundwaters, provided the extra Na and Ca that are necessary for the formation of mordenite. Various percentages of calcite are present in the altered tuffs. The enrichment of calcite in the altered tuffs indicates that thermal waters supply Ca, sourced from dissolution of Triassic carbonate rocks.

The alteration minerals in the Alaçatı (Çeşme) area do not seem to be laterally zoned. The occurrence of the zeolites seems to be related to inferred fracture zones trending NE—SW. These fracture zones are important because they provide porosity and permeability in the tuffs for zeolite formation. The large glass content and permeability of tuffs accompanied by the favorable hydrochemical condition resulted in zeolitization of the Alaçatı (Çeşme) area.

Permeability is often the limiting factor in clay-based barrier systems designed to attenuate miscible or immiscible contaminant transport. One critical aspect of barrier design is prediction of the effects of permeant conditions on physicochemical properties (e.g swelling) of the clay component and thus, ultimately, the permeability of the barrier. To this end, the permeability of an organically modified bentonite to ethanol-water solutions was determined to approximate the effects of organo sorption-induced swelling. The bentonite was modified with a substituted alkylammonium cation: benzyloctadecyl-dimethylammonium (BODMA). Powder X-ray diffraction (XRD) measurements were used to measure interlayer expansion and to estimate aggregate particle densities at any given ethanol concentration. Permeability measurements were conducted on samples under confining overburden stresses of 43 kPa (∼2.5 m of saturated soil) using a hydraulic gradient of ∼300. Sample thickness was continuously monitored during measurements of volumetric flow so that sample strain, void ratio and porosity could be calculated from changes in sample pore volumes. For calculations of porosity and void ratio, the swelling solid volume, determined from XRD, was assumed to include the sorbed layer (crystalline water/ethanol), the thickness of which is not normally considered in engineering applications. Exposure of the BODMA bentonite to increasing ethanol concentrations increased the swell volume of the clay. Measured coefficients of permeability for the BODMA bentonite decreased from ∼1 × 10−7m s−1 for pure water to ∼8 × 10−10m s−1 for pure ethanol. Exposure of the organo clay to ethanol-water solutions containing 0.2 M NaCl increased the effect of ethanol on clay swelling and permeability. Probable consequences of the effects of sorption-induced swelling on permeability and the performance of organo clay-based permeable reactive barriers are discussed.

X-ray basal reflections of several HDTMA-vermiculites show that when these contain co-adsorbed molecules of HDTMA-Br, their interlayer spacings are ∼29.5 Å. After HDTMA-Br has been leached out with ethanol, spacings decrease to ∼26 Å, but when exposed to toluene vapor the spacings increase to ∼36 Å, and to ∼45 Å in toluene liquid. Transmission X-ray diffraction photographs of HDTMA-vermiculites, both with and without co-adsorbed HDTMA-Br, indicate that they have highly ordered interlayer structures. The structure of HDTMA-Br-free vermiculite flakes is more open with the interlayer cations arranged in a 3a × b superstructure. In the HDTMA-Br containing HDTMA vermiculite flakes, HDTMA-Br molecules occupy interstitial positions between the HDTMA cations. Swelling in toluene vapor does not disorder the 2-dimensional arrangement of interlayer cations, but disorder does occur in toluene liquid. In toluene vapor, the aliphatic chains of the cations remain partially interdigitated, but in toluene liquid the interdigitation disappears. In response to the layer-charge density, the organization of the interlayer HDTMA units is caused by the self-assembly process responsible for hydrocarbon close packing.

The Markovian model of mixed-layering that has been used until now for the modeling of X-ray diffraction (XRD) patterns of 2:1 phyllosilicates describes the mixed-layer crystals as stacks of ‘layer units’ (LUs) that associate a 2:1 layer with an interlayer content. This model is not consistent when it is applied to a mixed-layer mineral (MLM) involving electrically charged layers, i.e. most of the mixed-layer phyllosilicates with 2:1 layers. Two consistent models can be proposed for these MLMs, which, instead of LUs, stack ‘interlayer units’ (IUs), composed of an interlayer content sandwiched between two half-layers. The IU-NPL model (interlayer units, non-polar layers) imposes non-polarity on the 2:1 layers resulting from the stack of these IUs, which implies restrictions on the succession of the IUs. In the other consistent model, the IU-PL one (interlayer units, polar layers), these restrictions are not imposed. These two models reproduce the Non-Polar 2:1 Layer Model and the Polar 2:1 Layer Model described by Altaner and Ylagan for illite-smectite mixed layering, and the second model corresponds to the stacks of O0.5 T I′ T O0.5 units described by Olives et al.

The present work points out the similarities and discrepancies of the calculated XRD patterns by using computer programs designed for the three models of mixed-layering (LU, IU-NPL and IU-PL) and for two-and three-component MLMs. Illustrations are provided for some I-S and I-S-V MLMs.

The IU-PL model leads to XRD patterns similar to those of the LU model. It is in agreement with lattice-energy calculations, expandability measurement, HRTEM imaging and NMR spectroscopy.

Submicroscopic intergrowths of K biotite, Na biotite and intermediate Na-K biotite from a schist near Málaga (Betic Cordilleras, Spain) were discovered using high-resolution transmission electron microscopy and analytical electron microscopy. The sample was also studied with X-ray diffraction, electron microprobe analysis, and scanning electron microscopy. Scanning electron microscopy revealed that the Na-enriched biotite is concentrated in albite-rich microdomains, albite being partially replaced by biotite. These images also revealed that both K and Na-K biotite grains appear locally retrograded to kaolinite. Transmission electron microscopic data indicated that K biotite, Na biotite and Na-K biotite form parallel or subparallel packets with interfaces parallel to the basal planes of biotite. Potassium biotite forms thick packets, chemically homogeneous, with a basal spacing of 10.1 Å. Sodium biotite also occurs as chemically homogeneous stacks of layers with a 9.78 Å periodicity. Sodium-K biotite shows, on the contrary, variable composition and basal spacings intermediate between K and Na biotites. Analytical electron microscopic data revealed important chemical differences between Na and K biotites, which affect both the tetrahedral and the octahedral sheets. Both electron microprobe analysis and analytical electron microscopy indicated that the trioctahedral micas show relatively low interlayer occupancy, suggesting the presence of H3O+ replacing the interlayer cations. Partial hydration of biotite explains the presence of a weak 14 Å reflection in the X-ray patterns. Both chemical and textural data suggested that these trioctahedral micas grew during a common prograde metamorphic episode, the phases with intermediate composition probably being metastable.

The dissolution kinetics of sepiolite in hydrochloric acid and nitric acid were studied in a batch reactor. The effects of reaction temperature, acid concentration, particle size and solid-to-liquid ratio on the dissolution process were investigated. Experimental studies were carried out in the ranges of 25–75°C for reaction temperature, 0.25–1.00 mol/L for acid concentration, 0.00755–0.05020 cm for average particle size and 2.5 to 12.5 g of solid/100 mL of acid for solid-to-liquid ratio. It was determined that the dissolution process is controlled by resistance of the diffusion through the product layer. The activation energies of the process were determined to be 40.8 and 38.3 kJ/mol for hydrochloric and nitric acid, respectively. The apparent rate constants were expressed as a function of reaction temperature, acid concentration, particle radius and solid-to-liquid ratio: kαe−4910(1/T)Cr−0.6 (s/l)−1 and kαe−4606(1/T)Cr−0.5 (s/1)−1 for hydrochloric and nitric acid, respectively; k is the apparent rate constant in min−1; T, the reaction temperature (K); C, the acid concentration (mol/L); r, the initial particle radius (cm); s/l, the solid-to-liquid ratio (g of solid/100 mL of acid).

The effect of an amphiphilic surfactanton the co-assembly of gibbsite and low-dimensional-order, liquid-crystalline mesophases using a hydrothermal-gelafion-devitrification route was examined. Crystal growth by this method occurred either in three dimensions or was limited to only two dimensions. Gibbsite and mesophases were synthesized using a cationic surfactant, cetyltrimethyl ammonium bromide (CTAB), as template and a commercial mineral sample as inorganic precursor. The commercial mineral sample contained pyrophyllite, α-quartz, and minor kaolinite. The syntheses were made at pH 10 under hydrothermal conditions followed by equilibration at room temperature. The hydrothermally soluble portion settled at room temperature to form a translucent hydrous gel. This translucent gel turned white after drying on a glass substrate because of the following events based on chemical analysis, X-ray diffraction, and optical/electron microscopy: (1) gibbsite preferentially nucleated at the gel/air and gel/glass interfaces to form spherulites of tabular gibbsite crystals with entrapped droplets; (2) a ∼26 Å basal-spacing, aluminate-encased, lamellar mesophase formed by 2D growth near the edge of the drying gel; and (3) residual solution in entrapped droplets within the gibbsite phase later devitrified abruptly into an optically isotropic material (an aluminosilicate gel possibly with minor mesophases) with a dendritic morphology. Formation of gibbsite and the lamellar mesophase was initially interface controlled, but later became 2D diffusion-controlled as CTAB concentrations and micelle lengths were increased with crystallization time. A relatively high surfactant/water ratio of the drying gel might account for predominant crystallization of an aluminate-encased lamellar mesophase rather than the hexagonal mesophase known as the Mobil Composition Material MCM-41.

Compositional data for 464 clay minerals (2:1 type) were analyzed by statistical techniques. The objective was to understand the similarities and differences between the groups and subgroups and to evaluate statistically clay mineral classification in terms of chemical parameters. The statistical properties of the distributions of total layer charge (TLC), K, VIAl, VIMg, octahedral charge (OC) and tetrahedral charge (TC) were initially evaluated. Critical-difference (P = 1%) comparisons of individual characteristics show that all the clay micas (illite, glauconite and celadonite) differ significantly from all the smectites (montmorillonite, beidellite, nontronite and saponite) only in their TLC and K levels; they cannot be distinguished by their VIAl, VIMg, TC or OC values which reveal no significant differences between several minerals.

Linear discriminant analysis using equal prior was therefore performed to analyze the combined effect of all the chemical parameters. Using six parameters [TLC, K, VIAl, VIMg, TC and OC], eight minerals groups could be derived, corresponding to the three clay micas, four smectites (mentioned above) and vermiculite. The fit between predicted and experimental values was 88.1%. Discriminant analysis using two parameters (TLC and K) resulted in classification into three broad groups corresponding to the clay micas, smectites and vermiculites (87.7% fit). Further analysis using the remaining four parameters resulted in subgroup-level classification with an 85–95% fit between predicted and experimental results. The three analyses yielded D2 Mahalanobis distances, which quantify chemical similarities and differences between the broad groups, within members of a subgroup and also between the subgroups. Classification functions derived here can be used as an aid for classification of 2:1 minerals.

Interstratified serpentine-smectite was found in the fine-grained fraction of altered metasomatic contact biotite-schists developed between serpentinite and granite-type rocks (Lower Silesia ophiolite sequence, Poland). Ni-rich serpentine-smectite is R0-interstratified lizardite (0.80)-stevensite (0.15)-vermiculite-like (0.05), with a coherent scattering domain (csd) of 5 layers (mean value). The Mg-rich variety of serpentine-smectite is R1 lizardite (0.80)-stevensite (0.20) with a csd size of 7 layers (mean value). A transmission electron microscope study revealed complex layer relationships, with zones composed of various serpentine-smectite packets having lizardite/smectite ratios of 3:1, 2:1, 1:1, 4:1 and scarce serpentine segregations. In both cases, the serpentine-smectites appear to be late products of alteration of the parent biotite-schist.

Experimental and calculated positions and intensities of reflections of the ethylene glycol-saturated, heated (250°C, thermal stage), and air-dried samples are in good agreement. Calculated X-ray diffraction patterns for interstratified glycolated and anhydrous serpentine-smectite are included in the Appendix.

Due to the importance of clay minerals in metal sorption, many studies have attempted to derive mechanistic models that describe adsorption processes. These models often include several different types of adsorption sites, including permanent charge sites and silanol and aluminol functional groups on the edges of clay minerals. To provide a basis for development of adsorption models it is critical that molecular-level studies be done to characterize sorption processes. In this study we conducted X-ray absorption fine structure (XAFS) and electron paramagnetic resonance (EPR) spectroscopic experiments on copper (II) sorbed on smectite clays using suspension pH and ionic strength as variables. At low ionic strength, results suggest that Cu is sorbing in the interlayers and maintains its hydration sphere. At high ionic strength, Cu atoms are excluded from the interlayer and sorb primarily on the silanol and aluminol functional groups of the montmorillonite or beidellite structures. Interpretation of the XAFS and EPR spectroscopy results provides evidence that multinuclear complexes are forming. Fitting of extended X-ray absorption fine structure spectra revealed that the Cu-Cu atoms in the multinuclear complexes are 2.65 Å apart, and have coordination numbers near one. This structural information suggests that small Cu dimers are sorbing on the surface. These complexes are consistent with observed sorption on mica and amorphous silicon dioxide, yet are inconsistent with previous spectroscopic results for Cu sorption on montmorillonite. The results reported in this paper provide mechanistic data that will be valuable for modeling surface interactions of Cu with clay minerals, and predicting the geochemical cycling of Cu in the environment.

Cronstedtite is a member of the kaolin-serpentine group. It yields a wealth of more or less disordered polytypes. The crystals of polytype 1T (space group P31m, a = 5.512, c = 7.106 Å) contain, within coherently scattering blocks, variable concentrations of stacking faults so that domains of the basic 3D periodic structure can be shifted by 1/3 (a2 − a1) or 1/3(a1 − a2). These so-called OD parallel intergrowths have been confirmed by high-resolution transmission electron microscopy. The effect manifests itself in the diffraction pattern so that reflections with h-k = 3n — the family reflections — are always sharp, whereas remaining reflections — the characteristic polytype reflections — may be smeared out parallel to c*. The intensities of the latter are thus underestimated during diffractometer measurements. An analysis of such multiple OD intergrowths reveals that the moduli of structure factors for all characteristic (i.e. non-family) polytype reflections are reduced relative to those calculated for the non-intergrown basic structure, by a common factor. This fact usually leads to the appearance of ghost peaks in Fourier maps and to their erroneous interpretation. The structure of the basic model can, however, be refined much better if two scale factors are assigned to the family and non-family reflections, respectively.

Manganese minerals are not common and the distinction of poorly crystalline Mn minerals from other associated minerals is important. For many years, the crystal structures of poorly crystalline Mn minerals in Fe/Mn concretions have been the subject of considerable conjecture and controversy. This study reports the micromorphological and mineralogical characteristics, and the chemical composition of Fe/Mn minerals in soft Fe/Mn concretions formed in Shimajiri Mahji soils (Typic Hapludalfs) that developed from Ryukyu limestone on Okinawa Island, Japan. The Fe/Mn minerals in brittle/soft Fe/Mn concretions were characterized using a sequential selective dissolution procedure (SSDP) by treatments with NaOH, hydroxylamine hydrochloride (HAHC) at 25°C and 60°C, and dithionite-citrate-bicarbonate (DCB) in combination with X-ray diffraction (XRD) and scanning electron microscopy (SEM). The HAHC treatment at 25°C dissolved birnessite, but not lithiophorite and goethite. A subsequent extraction with HAHC at 60°C dissolved lithiophorite but not goethite. Finally, the DCB treatment was able to dissolve goethite. The SEM images show that birnessite crystals, with a blade- or plate-like habit, form globular aggregates inside veins and cavities. Pseudo-hexagonal crystals of lithiophorite have produced thread-ball structures with crystal shape similar to birnessite and birnessite crystals are closely associated with lithiophorite. Well developed hexagonal plates of gibbsite crystals are clustered in different directions to make foliated vermiform structures. Aggregates of goethite crystals are acicular and are arranged into stars. The supplementary SSDP, in combination with XRD and SEM techniques, provides methods to distinguish and partly quantify birnessite and lithiophorite in the presence of layer silicate and Fe oxide minerals and confirm their own morphological features.