Consideration of XRD, TEM, AEM, and analytical data reported in the literature indicates that dioctahedral aluminous smectite and illite form two separate solid solutions that differ chemically from one another primarily by the extent of Al substitution for Si, the amount of interlayer K, and the presence of interlayer H2O. The data indicate that limited dioctahedral-trioctahedral and dioctahedral-vacancy compositional variations occur in both minerals. Excluding interlayer H2O and based on a half unit cell [i.e., O10(OH)2], natural dioctahedral smectite and illite solid solutions fall within the compositional limits represented by A0.3${\rm{R}}_{1.9}^{3 + }$Si4O10(OH)2-AR2+ R3+ Si4O10(OH)2-A0.25${\rm{R}}_{0.3}^{2 + }{\rm{R}}_{1.8}^{3 + }$Al0.25Si3.75O10(OH)2 for smectites and A0.8${\rm{R}}_{1.9}^{3 + }$Al0.5Si3.5O10(OH)2-A0.55${\rm{R}}_{0.45}^{2 + }{\rm{R}}_{1.55}^{3 + }$Al0.1Si3.9O10(OH)2-A0.9${\rm{R}}_{0.3}^{2 + }{\rm{R}}_{1.8}^{3 + }$Al0.9Si3.1O10(OH)2 for illites, where A represents either monovalent cations or divalent cations expressed as their monovalent equivalent (e.g., Ca2+/2); R2+ stands for the divalent cations Mg2+ and Fe2+ and R3+ refers to the trivalent cations Al3+ and Fe3+. Taking account of these compositional limits, smectite and illite solid solutions can be described in terms of nine and six thermodynamic components, respectively, all of which are consistent with both the law of definite proportions and the concept of a unit cell. Thermodynamic components that can be used to describe natural smectite solid solutions in terms of a half unit cell [i.e., O10(OH)2] can be expressed as NaAl3Si3O10(OH)2, NaAl3Si3O10(OH)2 ·4.5H2O, Al2Si4O10(OH)2, Fe2Si4O10(OH)2, Mg3Si4O10(OH)2, Fe3Si4O10(OH)2, K3AlSi4O10(OH)2, KAl3Si3O10(OH)2, and Ca0.5Al3Si3O10(OH)2. Of these, NaAl3Si3O10(OH)2 ·4.5H2O provides explicitly for the presence of interlayer H2O in the mineral. Thermodynamic components representing illite solid solutions in natural systems can be written for a half unit cell as KAl3Si3O10(OH)2, KMg3AlSi3O10(OH)2, KFe3AlSi3O10(OH)2, Al2Si4O10(OH)2, KFe2AlSi3O10(OH)2, and K3AlSi4O10(OH)2. The calculations and observations summarized below indicate that neither smectite nor illite occur in nature as stoichiometric phases and that the two minerals do not form a mutual solid solution corresponding to mixed-layered illite/smectite.

An organophilic bentonite was prepared by means of a reaction of natural Na-montmorillonite with trimethyldococylammonium which has an especially long n-alkyl chain. The addition of trimethyldococylammonium to montmorillonite was in the range 0.25–3.0 times the cation exchange capacity (CEC) of the clay (i.e. 0.23–2.82 mmol/g clay). The particle morphology in organic liquid suspensions of organoclay complexes was studied by measuring the viscosity based on Eyring’s rate process and Robinson’s relative sediment volume. In toluene, montmorillonite with 1.17 mmol/g clay trimethyldococylammonium (1.25 times the CEC) had the largest specific gel volume, relative sediment volume, and K-factor. The results of the stoichiometry for trimethyldococylammonium-montmorillonite show that practically all of the quaternary ammonium was adsorbed to montmorillonite. Maximum half widths of 001 reflections from X-ray diffraction patterns were obtained in the range 0.74–1.17 mmol/g clay, indicating a disordered arrangement of the organic cation molecules intercalated between the layers. Appreciable shifts to lower-frequency regions in the Fourier transform infrared absorption spectra as a result of CH2-stretching vibrations were observed with increasing amounts of the organic cation. When increasing the amount of organic cation added to the clay from 0.94 to 1.41 mmol/g clay, a large shift occurred to the lower-frequency side, approaching the frequency of the organic cation alone. This indicates that the interaction between adjacent hydrocarbon chains becomes progressively stronger, due to van der Waals attraction, with increases in the amount of organic cation. Interactions of the alkyl chains in trimethyldococylammonium-montmorillonite complexes with irregularly distributed and randomly arranged alkyl chains between the silicate layers were weak, and, as a result, solvation with external organic liquids occurred and gel formation developed through macroscopic swelling of the organoclay.

We investigated the compositions of a suite of 361 chrome-bearing spinels from spinel peridotites, ophiolitic mantle chromitites and from layered igneous intrusions in which the Fe2+/Fe3+ ratio has been determined by Mössbauer spectroscopy. We explore the crystal-chemical controls on the distribution of Fe3+ and on mineral stoichiometry with regard to electron-probe correction procedures for estimating Fe3+ in spinel. We find that chrome-bearing spinels can be subdivided into three groups: a Cr–Al-rich group; a high-Fe group; and a highly oxidised group. Spinels of the Cr–Al group are found in spinel peridotites and ophiolitic mantle chromitites. They are normal spinels with a low Fe3+ content and compositions that are close to stoichiometric. Spinels in the high-Fe group are found in layered igneous intrusions. They are also normal spinels which have higher concentrations of Fe3+ on the octahedrally coordinated site than is found for the Cr–Al group. Stoichiometric calculations tend to overestimate the Fe3+ content and their compositions do not conform to the MgO–cr# correlation found in the Cr–Al group. Spinels in the highly oxidised group are found in layered intrusions and ophiolitic mantle chromitites. They have (Fe3+/ΣFe)Möss > 0.4 and high Cr (cr# > 0.5), but relatively low Fe2+ (fe# 0.24–0.56). Stoichiometric calculations tend to underestimate the Fe3+ content. They represent normal spinels in which tetrahedrally coordinated Fe2+ has been oxidised to Fe3+.

Our data show that spinels with greater Cr and Fe are sufficiently different in their crystal chemistry from the aluminous spinels to indicate that the EPMA correction procedures developed for Fe3+ in aluminous spinels on the basis of the Cr/Al ratio, and used in oxy-thermobarometry, are inappropriate for Cr-rich and Fe-rich compositions.

Biochar is increasingly used in crop production as a fertilizer; however, its effects on nutrient cycling and stoichiometry in rice paddy soil–plant systems are unclear. We tested for effects of contrasting rates of biochar on soil and rice plant organ carbon (C), nitrogen (N), and phosphorus (P) concentrations and stoichiometry and soil physicochemical properties in early and late paddies. Overall, biochar reduced soil bulk density by an average of 7.4%, while application at 10, 20, and 40 t ha−1 increased soil C and N concentrations in early paddies by 31.6, 41.3, and 104.2%, respectively, and by 8.0, 5.0, and 21.8%, respectively; in late paddies, there were increases of 23.0, 94.1, and 117.0%, respectively, and 6.7, 15.4, and 18.0%, respectively (P < 0.05). Following biochar application at 10, 20, and 40 t ha−1, soil concentration of P decreased in early paddies by 10.9, 19.0, and 13.9%, respectively, and increased in late paddies by 4.3, 16.4, and 20.1%, respectively. Biochar increased ratios of soil C:N and C:P in early and late paddies (P < 0.05), and there was no effect on concentration and stoichiometry of soil available nutrients. Biochar reduced rice plant organ concentration of N and P in early rice and increased leaf N:P ratios. Despite the biochar application improved nutrient status in plant–soil system, we did not observe a significant increase in yield (P > 0.05). According to the N:P value of leaves between treatments, it was found that biochar alleviated the current situation of N limitation in paddy fields during the mature period and transformed the N limitation of early rice into a joint limitation of N and P. These results show that the addition of biochar to subtropical paddy soils leads to a short-term reduction in soil bulk density and increases in soil C and N concentrations and soil fertility. Thus, biochar applied at optimal rates is likely to improve the sustainability of subtropical paddy rice production.

Cu-doping and crystallographic site occupations within the half-Heusler (HH) TiNiSn, a promising thermoelectric material, have been examined by atom probe tomography. In particular, this investigation aims to better understand the influence of atom probe analysis conditions on the measured chemical composition. Under a voltage-pulsing mode, atomic planes are clearly resolved and suggest an arrangement of elements in-line with the expected HH (F-43m space group) crystal structure. The Cu dopant is also distributed uniformly throughout the bulk material. For operation under laser-pulsed modes, the returned composition is highly dependent on the selected laser energy, with high energies resulting in the measurement of excessively high absolute Ti counts at the expense of Sn and in particular Ni. High laser energies also appear to be correlated with the detection of a high fraction of partial hits, indicating nonideal evaporation behavior. The possible mechanisms for these trends are discussed, along with suggestions for optimal analysis conditions for these and similar thermoelectric materials.

Soil degradation is characterized by loss of soil organic matter, decline in fertility, imbalance in elemental content, deterioration of soil structure, and overall a deterioration of soil environment. According to the classification method of Pieri et al. (1992), the soil is classified into different degradation classes by calculating the soil structural stability index (St) of each sample point. We aimed to investigate changes in the contents, storages and stoichiometry of soil carbon (C), nitrogen (N), and phosphorus (P) together with changes in soil physical traits along a soil degradation gradient in jasmine croplands in Fuzhou area (China). The content and storage of soil C and N decreased with increasing intensity of land degradation. Soil organic C content was 15.4%, 32.3%, and 38.8% lower, respectively, in the low, medium, and high degree of degradation soils, than in the nondegraded soils. The soil C:N ratio was 18.5% higher in soils in the middle degree of degradation than in the nondegraded soils. Compared with nondegraded soils, the bulk density of the degraded soils increased and water content decreased. The decrease of soil pH coupled with salinity (conductivity) and the loss of aggregate stability are the main traits that distinguish degraded from nondegraded soils. We also detected a general N and P deficiency that is aggravated by the degradation process. Unreasonable management easily leads to degradation associated with a loss of organic C and total soil nutrients, thus impairing even more a general N and P deficiency in this area. Therefore, higher inputs of organic fertilizer should be added to alleviate the lack of organic matter, and appropriate burial should be conducted to reduce nutrient loss. Moreover, a rise of N and P fertilizer application is also advisable.

A structure hierarchy is developed for chain-, ribbon- and tube-silicate based on the connectedness of one-dimensional polymerisations of (TO4)n− tetrahedra, where T = Si4+ plus P5+, V5+, As5+, Al3+, Fe3+, B3+, Be2+, Zn2+ and Mg2+. Such polymerisations are described by a geometrical repeat unit (with ng tetrahedra) and a topological repeat unit (or graph) (with nt vertices). The connectivity of the tetrahedra (vertices) in the geometrical (topological) repeat units is denoted by the expression cTr (cVr) where c is the connectivity (degree) of the tetrahedron (vertex) and r is the number of tetrahedra (vertices) of connectivity (degree) c in the repeat unit. Thus cTr = 1Tr12Tr23Tr34Tr4 (cVr = 1Vr12Vr23Vr34Vr4) represents all possible connectivities (degrees) of tetrahedra (vertices) in the geometrical (topological) repeat units of such one-dimensional polymerisations. We may generate all possible cTr (cVr) expressions for chains (graphs) with tetrahedron (vertex) connectivities (degrees) c = 1 to 4 where r = 1 to n by sequentially increasing the values of c and r, and by ranking them accordingly. The silicate (sensu lato) units of chain-, ribbon- and tube-silicate minerals are identified and associated with the relevant cTr (cVr) symbols. Following description and association with the relevant cTr (cVr) symbols of the silicate units in all chain-, ribbon- and tube-silicate minerals, the minerals are arranged into decreasing O:T ratio from 3.0 to 2.5, an arrangement that reflects their increasing structural connectivity. Considering only the silicate component, the compositional range of the chain-, ribbon- and tube-silicate minerals strongly overlaps that of the sheet-silicate minerals. Of the chain-, ribbon- and tube-silicates and sheet silicates with the same O:T ratio, some have the same cVr symbols (vertex connectivities) but the tetrahedra link to each other in different ways and are topologically different. The abundance of chain-, ribbon- and tube-silicate minerals decreases as O:T decreases from 3.0 to 2.5 whereas the abundance of sheet-silicate minerals increases from O:T = 3.0 to 2.5 and decreases again to O:T = 2.0. Some of the chain-, ribbon- and tube-silicate minerals have more than one distinct silicate unit: (1) vinogradovite, revdite, lintisite (punkaruaivite) and charoite have mixed chains, ribbons and/or tubes; (2) veblenite, yuksporite, miserite and okenite have clusters or sheets in addition to chains, ribbons and tubes. It is apparent that some chain-ribbon-tube topologies are favoured over others as of the ~450 inosilicate minerals, ~375 correspond to only four topologically unique graphs, the other ~75 minerals correspond to ~46 topologically unique graphs.

The structure hierarchy hypothesis states that structures may be ordered hierarchically according to the polymerisation of coordination polyhedra of higher bond-valence. A hierarchical structural classification is developed for sheet-silicate minerals based on the connectedness of the two-dimensional polymerisations of (TO4) tetrahedra, where T = Si4+ plus As5+, Al3+, Fe3+, B3+, Be2+, Zn2+ and Mg2+. Two-dimensional nets and oikodoméic operations are used to generate the silicate (sensu lato) structural units of single-layer, double-layer and higher-layer sheet-silicate minerals, and the interstitial complexes (cation identity, coordination number and ligancy, and the types and amounts of interstitial (H2O) groups) are recorded. Key aspects of the silicate structural unit include: (1) the type of plane net on which the sheet (or parent sheet) is based; (2) the u (up) and d (down) directions of the constituent tetrahedra relative to the plane of the sheet; (3) the planar or folded nature of the sheet; (4) the layer multiplicity of the sheet (single, double or higher); and (5) the details of the oikodoméic operations for multiple-layer sheets. Simple 3-connected plane nets (such as 63, 4.82 and 4.6.12) have the stoichiometry (T2O5)n (Si:O = 1:2.5) and are the basis of most of the common rock-forming sheet-silicate minerals as well as many less-common species. Oikodoméic operations, e.g. insertion of 2- or 4-connected vertices into 3-connected plane nets, formation of double-layer sheet-structures by (topological) reflection or rotation operations, affect the connectedness of the resulting sheets and lead to both positive and negative deviations from Si:O = 1:2.5 stoichiometry. Following description of the structural units in all sheet-silicate minerals, the minerals are arranged into decreasing Si:O ratio from 3.0 to 2.0, an arrangement that reflects their increasing structural connectivity. Considering the silicate component of minerals, the range of composition of the sheet silicates completely overlaps the compositional ranges of framework silicates and most of the chain-ribbon-tube silicates.

The functional properties of the high-temperature superconductor Y1Ba2Cu3O7−δ (Y-123) are closely correlated to the exact stoichiometry and oxygen content. Exceeding the critical value of 1 oxygen vacancy for every five unit cells (δ>0.2, which translates to a 1.5 at% deviation from the nominal oxygen stoichiometry of Y7.7Ba15.3Cu23O54−δ) is sufficient to alter the superconducting properties. Stoichiometry at the nanometer scale, particularly of oxygen and other lighter elements, is extremely difficult to quantify in complex functional ceramics by most currently available analytical techniques. The present study is an analysis and optimization of the experimental conditions required to quantify the local nanoscale stoichiometry of single crystal yttrium barium copper oxide (YBCO) samples in three dimensions by atom probe tomography (APT). APT analysis required systematic exploration of a wide range of data acquisition and processing conditions to calibrate the measurements. Laser pulse energy, ion identification, and the choice of range widths were all found to influence composition measurements. The final composition obtained from melt-grown crystals with optimized superconducting properties was Y7.9Ba10.4Cu24.4O57.2.

In order to understand the stoichiometric balance between foliar nitrogen (N) and phosphorus (P) on P-poor soils, we investigated how foliar N and P attributes (i.e. N and P concentrations in green and senesced leaves, N and P resorption efficiencies) of 30 tropical tree species co-vary along a gradient of soil P availability across three forests on Mount Kinabalu, Borneo. We found strong and positive correlations between foliar N and P in the concentrations and resorption efficiencies within each forest and across the three forests. Slopes of standardized major axis between foliar N and P concentrations for both green and senesced leaves were not different among the three forests, although the values of the scaling exponent in the relationships of foliar N to P across the three forests were significantly lower than 1. We suggest that down-regulation of N concentrations in green leaves on P-poor soils is one of several possible mechanisms explaining why N concentrations decrease with decreasing P concentrations in both green and senesced leaves toward a lower P availability in soils. On the other hand, the physiological and ecological reasons why N and P resorption efficiencies are positively correlated with each other across tree species remain unclear.

This paper describes the development of a method for quantitative measurement of the elemental composition of particulate matter (PM) in seawater. This method is based on use of wavelength dispersive X-ray fluorescence (WDXRF) analysing PM harvested on various filter types. As the amount of material is less than a monolayer of cells on the filters we reduced the need for absorption correction. Given the appropriate combination of filters and elements the detection limits are low: <1 µg/filter for carbon (C), nitrogen (N), and <0.1 µg/filter for silicon (Si), phosphorus (P), calcium (Ca) and iron (Fe). The analytical range used was 90–750 µg C, 23–116 µg N and 7–30 µg P, depending on the filters applied. Calibration constants for the elements included in this study were obtained from analysis of known quantities of chemical compounds on filters or silver plates. For carbon and nitrogen we also used comparative measurements of Synechococcus sp. cultures by CHN analyser and WDXRF. We harvested PM from 150 ml to 2000 ml on each filter in three replicates, obtaining less than 5% analytical variability between the replicates. One of the challenges using WDXRF as proposed here is the absorption of X-ray signals by the filter and variability of cell/particle sizes, and, consequentlyly, the variability of harvested PM on various filters. We find that an anodisc filter is best suited for C and N, while polycarbonate filters are best for heavier elements. Here we present analytical details and some data from field experiments related to C, N, P, Si, Ca and Fe in particles from seawater.

Electron energy loss spectra in conjunction with near-edge fine structures of purely stoichiometric niobium monoxide (NbO) and niobium pentoxide (Nb2O5) reference materials were recorded. The structures of the niobium oxide reference materials were checked by selected area electron diffraction to ensure a proper assignment of the fine structures. NbO and Nb2O5 show clearly different energy loss near-edge fine structures of the Nb-M4,5 and -M2,3 edges and of the O-K edge, reflecting the specific local environments of the ionized atoms. To distinguish the two oxides in a quantitative manner, the intensities under the Nb-M4,5 as well as Nb-M2,3 edges and the O-K edge were measured and their ratios calculated. k-factors were also derived from these measurements.

Discrete humus layers are common on podzols under temperate coniferous and tropical heath forests, and patchy layers also occur under some temperate broadleaved forests on non-podzolic soils. We used multiple data sets to test the reported association of humus with oligotrophic but non-podzolic soils under non-heath dipterocarp forest at Lambir, Sarawak. We examined the distribution, morphology and nutrient dynamics of necromass on soils derived from sandstone and shale. Concentrations of the main mineral nutrients were lower in fresh litter on the very oligotrophic sandstone soils than on shale. The rates of litterfall were similar, so that annual litterfall fluxes of all nutrients were lower on sandstone. The lower nutrient concentrations and fluxes in the litter on sandstone resulted in slower decomposition, longer residence times and larger standing crops of forest-floor necromass, with lower concentrations of nutrients. The necromass on sandstone sequestered significantly more N, K and Mg but less Ca and Mn than on shale, with no significant difference for P. The variations in necromass nutrient dynamics were associated with morphological differences. There were mats of densely rooted humus under the litter on sandstone, whereas litter lay directly over the mineral topsoil on shale. Spatial associations with soil nutrients were weak for necromass thickness, but clear for humus. The proportions of nutrients in the litterfall and necromass reflected the stoichiometric profiles of the soils. We attribute the differences in necromass nutrient dynamics and their association with soil reserve nutrients to lower rates of nutrient replenishment from the weathering of sandstone than from shale. Necromass characteristics are robust field indicators of multivariate edaphic differences in these and other tropical forests on Acrisols/Ultisols derived from Tertiary clastic sediments.

Astrobiology is an extremely wide-ranging field and thus is in special need of conceptual and theoretical frameworks that can integrate its various arenas of study. In this paper I review recent work associated with a conceptual framework known as ‘ecological stoichiometry’ and even more recent extensions in the development of ‘biological stoichiometry’. Ecological stoichiometry is the study of the balance of energy and multiple chemical elements in ecological interactions and has developed rapidly in the study of nutrient cycling and energy flow in aquatic food webs. It identifies the elemental composition of interacting biota as central in understanding the nature of their interactions and dynamics, including key feedbacks via nutrient recycling. Biological stoichiometry extends this mode of thinking to all types of biological systems. It especially seeks to better understand, at the biochemical and genetic levels, the factors influencing the elemental composition of living things and the evolutionary forces that drive and constrain that elemental composition. By connecting key concepts of ecosystem ecology, evolutionary biology and biochemistry, stoichiometric theory integrates biological information into a more coherent whole that holds considerable promise for application in astrobiology. Several examples of potential astrobiological applications of stoichiometric analysis are offered, including ones related to pre-biotic evolution, the Cambrian explosion, biosignatures and biological feedbacks on planetary carbon cycling.