Weathering rind formation in buried terrace cobbles during periods of up to 300ka

Weathering rinds formed in Mesozoic sandstone and basalt cobbles buried in terrace deposits for up to 300 ka have been investigated. The aim was to determine the formation process and elemental mass balances during rind development. The ages of terraces distributed in the western part of Fukui prefecture, central Japan have been determined as 50 ka, 120 ka and 300 ka based on a tephro-stratigraphic method. Detailed investigations across the weathering rinds, consisting of microscopic observations, porosity measurements, and mineralogical and geochemical analyses using X-ray diffractometry (XRD), X-ray fluorescence (XRF), secondary X-ray analytical microscopy (SXAM), scanning electron microanalyser (SEM) and electron probe microanalysis (EPMA) have been carried out. The results revealed that the Fe concentrations in the weathering rind of a basalt cobble slightly decreased from the cobble’s surface (rim) towards the unweathered core. In contrast, in a sandstone cobble formed under the same environmental conditions over the same period of time there is an Fe-rich layer at some distance below the cobble’s surface. Elemental mass balances across the rinds were determined by using open system mass balance (τ_i,j) calculations and show that the Fe was precipitated as Fe-oxyhydroxides in the basalt cobbles, although Fe was slightly removed from the rims. In sandstone cobbles, on the other hand, Fe migrated along a Fe concentration gradient by diffusion and precipitated as Fe-oxyhydroxide minerals to form the weathering rinds. Presumably, precipitation was due to the relatively higher pH conditions caused by mineral dissolution within the pores, principally involving calcite, but probably also silicates including feldspar. The detailed characterization of the weathering rinds revealed the influence of lithology on the accumulation and dissolution of Fe-oxyhydroxides, causing weathering rinds with different characteristics to develop in different kinds of buried cobbles under the same conditions. Relatively large climatic changes in the study area did not cause discernable variations in the mean formation rates of the studied rinds, which were in the order of 10^?8 m/a for both basalt and sandstone cobbles. These rates are 1–2 orders of magnitude slower than those reported for tropical areas elsewhere, most probably due to the lower rainfall in the studied area.     

Evolution of Eastern Ghats granulite belt of India in a compressional tectonic regime and juxtaposition against Iron Ore Craton of Singhbhum by oblique collision — transpression

Three major episodes of folding are evident in the Eastern Ghats terrain. The first and second generation folds are the reclined type; coaxial refolding has produced hook-shaped folds, except in massif-type charnockites in which non-coaxial refolding has produced arrow head folds. The third generation folds are upright with a stretching lineation parallel to subhorizontal fold axes. The sequence of fold stylesreclinedF ₁and coaxialF ₂, clearly points to an early compressional regime and attendant progressive simple shear. Significant subhorizontal extension duringF ₃folding is indicated by stretching lineation parallel to subhorizontal fold axes. In the massif-type charnockites low plunges ofF ₂folds indicate a flattening type of deformation partitioning in the weakly foliated rocks (magmatic ?). The juxtaposition of EGMB against the Iron Ore Craton of Singhbhum by oblique collision is indicative of a transpressional regime.     

The superstructure of plagioclase feldspars

A modulation function representing the position and density of (Na, Ca) atoms in the superstructure of the e-plagioclase has been derived from the average structures of different plagioclase and a general modulation theory. Based on this function the superstructure of bytownite (An₇₃) has been studied with the single crystal X-ray method. The cell dimensions by Megaw's axes are a=7.946(3)A, b=67.09(2)A, c=12.236(4)A, α=39.03(1)°, β=45.63(1)° and γ=59.63(1)°. Z=18(Na, Ca) Al(Al, Si)Si₂O₈. The initial phase factor of the modulation function for bytownite has been obtained from the intensity data of the satellite reflections. This modulation function indicates a coherent small-scale alternation of the Na-rich and Ca-rich bands in the superstructure. This superstructure has been refined by applying the albite and anorthite structures to the Na-rich and Ca-rich bands, respectively. The change of the superstructure of the e-plagioclase due to the compositional change has been described based on the movements of the satellites in reciprocal space. The direction of the coherent small-scale intergrowth of the anorthite-like and albite-like bands is perpendicular to the t vector. The thickness of the intergrowth is 1/|t|. Both direction and thickness change regularly from An₇₅ to An₂₅.     

The relationship between slope gradient and lateritic cobble orientation with respect to shape, northwestern Taiwan

In situ investigations of lateritic cobble slopes have demonstrated that where the grain orientation is more uniform, the anisotropy is more obvious. Grain orientation will also affect the slope gradient and slope surface. The slope forms an escarpment when the intersection between the cobble orientation strike and the slope surface ranges between 90 and 180°. By contrast, there is a dip-slope geometry when the angle of intersection is 0°. The slope gradient increases and has an angle of 50 to 80° when the intersected angle ranges from 0 to 180°. The results indicate a positive relationship between these two factors. The slope grade will increase when the disk and bladed grain shape of the cobbles increase their percentage relative to the material composition. On the other hand, the slope gradient decreases when the proportion of equant and roller grain shapes of cobble increase in the composition.     

Evaluation of thermochemical data on Fe-Mg olivine,orthopyroxene, spinel and Ca-Fe-Mg-Al garnet

Thermochemical data on Fe-Mg olivine, orthopyroxene, spinel and Ca-Fe-Mg garnet have been tested and reevaluated in reproducing experimental equilibrium data. All data (except of spinel) adjusted in this process lie within the error limits of original calorimetric experiments. For spinel, an enthalpy of −2307.2 kJ/mol and an entropy of 81.5 J/mol-K has been recommended. Recommended interaction parameters for the spinel-hercynite and forsterite-fayalite solutions are as follows:Spinel: W_{spinel-hercynite} = 9124.0 J/mol. W_{hercynite-spinel} = 0.0 J/molOlivine: W = 4500.0 J/mol for 1 cation.Excess entropies (on 1 cation basis) necessary to reproduce phase equilibria for the pyrope-almandine and almandine-grossular solutions are as follows:Mg-Fegarnet: W^s_{pyrope-almandine} = 11.760 − 0.00167 J/mol-K. W^s_{almandine-pyrope} = −10.146 +0.0037T J/mol-K.Fe-Ca garnet: W^s = −16.07 + 0.0126T J/mol-K.     

年轻冰川沉积砾石的晒退特征及其对岩石释光埋藏测年的启示

不完全晒退/晒退不均现象是冰川沉积物释光测年所面临的巨大挑战,这一问题限制了传统颗粒沉积物释光方法在冰川沉积物测年方面的应用。最新发展的岩石释光埋藏测年技术,可以根据释光-深度曲线判断砾石是否经历过充分曝光,是解决冰川沉积晒退不均问题的有效途径之一。本工作选择青藏高原东部硬普沟现代冰川前沿为研究对象,采集130个年轻冰川沉积砾石样品,包括93个现代样品和37个小冰期样品,其中20个现代样品采自地表。首先,运用表_{~2 mm}/饱和信号法区分不同冰川沉积环境中砾石样品的晒退程度;再基于SAR和SGC法初步估算样品的等效剂量及其高估情况;然后,统计砾石样品的特征（磨圆度、球度、颜色、晶粒大小、晶粒相对大小、砾石大小等）与晒退程度的关系,找寻晒退良好的砾石及其特征。结果表明大部分采样点的砾石样品呈现了被晒退的特征,平均20.6%的埋藏砾石的岩芯晒退良好,剂量高估程度低;不同沉积类型样品的晒退程度不一,侧碛垄顶部砾石样品晒退程度最好,冰水阶地和现代冰河砾石样品次之,现代冰川后退碛垄间洼地的冰水沉积砾石样品晒退程度最差,剂量高估较严重;磨圆度较差、球度较低、浅色的花岗岩砾石晒退程度较好。综上,冰川沉积砾石的晒退程度与沉积环境、沉积过程、搬运距离、砾石特征等相关,在进行岩石释光埋藏测年采样时,应综合考虑上述情况。     

High-pressure crystal chemistry of chromous orthosilicate, Cr2SiO4. A single-crystal X-ray diffraction and electronic absorption spectroscopy study

The high-pressure behaviour of chromous orthosilicate, Cr₂SiO₄, has been studied by means of single-crystal X-ray diffraction and electronic absorption spectroscopy. X-ray diffraction data show that the structure remains orthorhombic to the highest pressure reached of 9.22?GPa. The compressibility of the unit-cell is strongly anisotropic with the c axis approximately six times more compressible than the a and b axes. A third-order Birch-Murnaghan equation of state fitted to the volume-pressure data yields V ₀?=?610.10(3)?ų, K = 94.7(4)?GPa, K′?=?8.32(14). Cr₂SiO₄ is therefore more compressible than the isostructural Cd analogue, even though its molar volume is smaller. This unusual behaviour can be attributed to the fact that the Cr atom is too small for the six-coordinated site that it occupies, and the site is therefore strongly distorted. Structure refinements indicate that under high pressures the Cr atom remains strongly displaced from the central position of the octahedron. Polarized and unpolarized electronic absorption spectra include a strong absorption band occuring at 18.300 cm^?1 for E//c (which is parallel to the shortest Cr-Cr vector in the structure) which has an unusually large half width (5000?cm^?1), indicative of electronic interaction between metal centres. Deconvolution of unpolarized high-pressure spectra show that the relative integrated intensity of this component increases linearly from 40% at 1?bar to 60% at 11.2?GPa. Both the structural changes and the absorption spectra at high pressures suggest that pairs of adjacent Cr atoms in chromous orthosilicate form chromium dimers with a weak metal-metal bond, which is consistent with the diamagnetic response found at ambient pressure.     

Progressive deformation and the rotation of contemporary fold axes in the Ballybofey Nappe,north-west Ireland

Internal regions of orogenic belts may be characterized by an alignment of fold axes with mineral elongation lineations. This relationship is commonly interpreted as representing progressive tightening and rotation towards the shear direction of early buckle folds, the hinges of which were initiated orthogonal to this direction. Detailed structural analysis of lower amphibolite facies Dalradian metasediments of the Ballybofey (fold) Nappe, north-west Ireland, shows that an intense S₃ schistosity is developed axial planar to mesoscopic and minor F₃ folds. In areas of low D₃ strain, F₃ fold axes plunge gently towards the north-east, whereas in regions of greater strain plunges are towards the south-east subparallel to the constant mineral lineation. Minor folds which initiated at angles of 70–80° from the mineral lineation subsequently rotated towards the shear direction in a consistent clockwise sense. Progressive and variable non-coaxial deformation oblique to the original mean F₃ orientation has resulted in a unimodal distribution pattern of fold axes. Analysis of the angular rotation of fold axes enables estimates of the bulk shear strain to be evaluated and models of progressive deformation to be assessed.     

Deformed graptolites, finite strain and volume loss during cleavage formation in rocks of the taconic slate belt, New York and Vermont, U.S.A.

An analysis of graptolites in the Taconic slate belt of eastern New York and western Vermont (U.S.A.) shows that they are nearly ideal strain markers. For the three species used in this study, Orthograptus whitfieldii, Orthograptus calcaratus and Climacograptus bicornis, the spacing of thecae is constant except for the first five or so thecae in the proximal part of the fossil rhabdosome. Further, the thecal apertures are perpendicular to the long axis of the stipe. Observations of the thecal spacing in deformed rocks leads to a determination of extension (e=(l_f−l₀)/l₀) and a measure of the angle between thecal aperture and stipe axis yields a direct determination of angular shear strain. In practice, we find it is most straightforward to use length changes to determine the magnitude of principal strains. In Taconic slates, e₁ ranges from 1.0 to 0.24, e₂ ranges from 0.23 to −0.43 and e₃ ranges from −0.56 to −0.74. Thus, we find that the absolute finite strain in these slates is constrictional at three sites, plane strain at another and a true flattening at only one site. An examination of volume changes based on strain results in determinations of between 81% volume loss and 7% volume gain, with volume losses between 28% and 81% in 9 out of 10 calculations. These conclusions are in accord with previous determinations of volume loss based on reduction spot analyses and are consistent with the observation that pressure dissolution was a common grain scale deformation process in cleavage formation but that these slates lack abundant veins, fibrous overgrowths or other identifiable sites of reprecipitation.     

How tightly does calcite e-twin constrain stress?

Mechanical twinning along calcite e-planes has been used for paleostress analyses. Since the twinning has a critical resolved shear stress at ∼10 MPa, not only principal stress axes but also differential stress can be determined from the twins. In this article, five-dimensional stress space used in plasticity theory was introduced to describe the yield loci of calcite e-twinning. The constraints to paleostress from twin and untwin data and from calcite grains twinned on 0, 1, 2 and 3 e-planes were quantified by using their information contents, which were defined in the stress space. The orientations of twinned and untwinned e-planes are known to constrain not only stress axes but also differential stress, D, but they loose the resolution of D if the twin lamellae were formed at D greater than 50–100 MPa. On the other hand, it is difficult to observe twin lamellae subparallel to a thin section. The stochastic modeling of this effect showed that 20–25% of twin lamellae can be overlooked. The degradation of the constraints by this sampling bias can be serious especially for the determination of D.     

Oolite deformation in Windgällen, Canton Uri, Switzerland

Detailed analysis of the oolite deformation in Windgällen revealed that the finite-strain states vary significantly and systematically over the major recumbent structures. The strain is lowest at the fold cores and highest along the limbs, which have suffered extensions of up to 150%. These high strains are interpreted as the result of strong overfolding during the development of the nappe-like structure. The maximum ratio of the strain ellipsoids computed from the oolite shapes is 14.6:1, though individual oolites having axial ratios as high as 30 : 1 have been encountered. The intermediate axes of the strain ellipsoids throughout the area have been extended between 3 and 64% and the strain ellipsoids are of the flattening type with K being less than unity. The pre-deformation fabric of the oolites is very weak and their initial axial ratios in any two-dimensional section is generally less than 2:1. Slaty cleavage is coincident with the plane of maximum compression in the rock. The relationship of cleavage, folds and oolite deformation suggest that cleavage develops progressively during deformation and forms at the same time as the folds associated with it.     

Neoichnology of Chalk cobbles from north Norfolk,England: implications for taphonomy and palaeoecology

The study of marine biota of the North Sea from the perspective of its relevance to palaeontology (Aktuopaläontologie) has enabled modern patterns and processes to be identified that can also be recognised in ancient communities. A collection of Chalk cobbles from the coast of north Norfolk, eastern England, preserves a limited ichnofauna: Gastrochaenolites ornatus Kelly and Bromley; Gastrochaenolites isp.; and Caulostrepsis isp. All cobbles show evidence of physical modification (corrasion) since they were bored; no Gastrochaenolites is complete and no clast has Caulostrepsis on all sides, therefore clasts have been corraded subsequent to boring. Only one producing organism in Gastrochaenolites, probably Barnea sp., is preserved in situ. Gastrochaenolites borings were infested by a range of encrusting organisms after the demise (and removal of shells) of the boring bivalves: thread-like algae; agglutinated worm tubes; cheilostome bryozoan Cryptosula pallasiana (Moll); and serpulids Hydroides norvegica Gunnerus and Pomatoceras triqueter (Linnaeus). Such a suite of encrusting organisms would be impossible to see in a fossil boring filled with lithified sedimentary rock unless it was released by dissolution of the substrate. Such cobbles, corraded since they were infested by borers, leave only portions of traces for identification, commonly only to ichnogenus.     

Occurrence and influence of residual gas released by crush methods on pore structure in Longmaxi shale in Yangtze Plate,Southern China

The composition of gas released under vacuum by crushing from the gas shale of Longmaxi Formation in Upper Yangtze Plate, Southern China was systematically investigated in this study. The effect of residual gas release on pore structures was checked using low-pressure nitrogen adsorption techniques. The influence of particle size on the determination of pore structure characteristics was considered. Using the Frenkel-Halsey-Hill method from low-pressure nitrogen adsorption data, the fractal dimensions were identified at relative pressures of 0−0.5 and 0.5−1 as D₁ and D₂, respectively, and the evolution of fractal features related to gas release was also discussed. The results showed that a variety component of residual gas was released from all shale samples, containing hydrocarbon gas of CH₄ (29.58% −92.53%), C₂H₆ (0.97% −2.89%), C₃H₈ (0.01% −0.65%), and also some non-hydrocarbon gas such as CO₂ (3.54% − 67.09%) and N₂ (1.88%−8.07%). The total yield of residual gas was in a range from 6.1 μL/g to 17.0 μL/g related to rock weight. The geochemical and mineralogical analysis suggested that the residual gas yield was positively correlated with quartz (R²=0.5480) content. The residual gas released shale sample has a higher surface area of 17.20−25.03 m²/g and the nitrogen adsorption capacity in a range of 27.32−40.86 ml/g that is relatively higher than the original samples (with 9.22−16.30 m²/g and 10.84−17.55 ml/g). Clearer hysteresis loop was observed for the original shale sample in nitrogen adsorption-desorption isotherms than residual gas released sample. Pore structure analysis showed that the proportions of micro-, meso- and macropores were changed as micropores decreased while meso- and macropores increased. The fractal dimensions D₁ were in range from 2.5466 to 2.6117 and D₂ from 2.6998 to 2.7119 for the residual gas released shale, which is smaller than the original shale. This factor may indicate that the pore in residual gas released shale was more homogeneous than the original shale. The results indicated that both residual gas and their pore space have few contributions to shale gas production and effective reservoir evaluation. The larger fragments samples of granular rather than powdery smaller than 60 mesh fraction of shale seem to be better for performing effective pore structure analysis to the Longmaxi shale.     

The rotation of garnet porphyroblasts around a single fold, Lukmanier Pass, Central Alps

The orientation of the straight internal foliation S_i within large ( 5 mm) garnet porphyroblasts has been measured relative to the orientation of the external foliation S_e around a single antiform of 0.5 m wavelength, which folds the dominant regional foliation. The internal foliation is not constant in orientation, but varies consistently both with position around the fold and with the porphyroblast ellipticity. The dip of S_i (hinge dip taken as zero) is consistently less than the dip of S_e; it increases with increasing dip of S_e and with increasing ellipticity of the porphyroblasts. S_i effectively defines a fold with an opening angle greater than that in the external foliation. The opening angle of this fold in S_i decreases with increasing porphyroblast ellipticity. The observed variation in the orientation of S_i can be explained qualitatively by a flattened flexural flow model for fold development, as could be expected for folding of a pre-existing, strongly anisotropic foliation. The measurements clearly demonstrate that rotation of porphyroblasts relative to geographical co-ordinates did occur during the development of this fold and that a model based on the classical theories of rotation of stiff inclusions in a weaker viscous matrix is most appropriate.     

Orebody geometry in lode gold deposits from Zimbabwe: implications for fluid flow,deformation and mineralization

The geometry of some orebodies can be described simply and accurately by three orthogonal axes, U≥V≥W. The ratios between these axes can be expressed as a parameter j=(U/V−1)/(V/W−1), and represented by a graph of U/V plotted against V/W, analogous to the treatment of strain ellipsoids. The orientations of orebodies can be plotted simply on projections using the UVW axes. Measurements of ore bodies from two examples of lode gold deposits from the Zimbabwe craton show that most of these orebodies are oblate. However, orebodies can have significant U/V ratios, implying a component of pipe-like fluid flow during mineralization. Pipe flow is demonstrated to be orders of magnitude more conductive than flow in planar veins and faults. There are significant variations in orebody geometry between deposits and within different sections of a single deposit. W values appear to be influenced by host rock: more permeable rocks have higher W. A negative trend of j value with orebody volume indicates that orebodies do not evolve in a self-similar way, but tend to more oblate shapes with increasing volume.     

Transverse fold evolution in the External Sierra,southern Pyrenees,Spain

Fault-slip data are used to reconstruct varying tectonic regimes associated with transverse fold development along the eastern and southern margins of the Jaca basin, southern Pyrenees, Spain. The Spanish Pyrenean foreland consists of thrust sheets and leading-edge décollement folds which developed within piggyback basins. Guara Formation limestones on the margins of the Jaca basin were deposited synchronously with deformation and are exposed in the External Sierra. Within the transverse folds, principal shortening axes determined from P and T dihedra plots of fault-slip data show a shift from steep shortening in stratigraphically older beds to NNE–SSW horizontal shortening in younger beds. Older strata are characterized by extensional faults interpreted to result from halotectonic (salt tectonics) deformation, whereas younger strata are characterized by contraction and strike-slip faults interpreted to result from thrust sheet emplacement. The interpretation of the timing for the shortening axes in the younger strata is supported by the observation that these axes are parallel to shortening axes determined from finite strain analysis, calcite twins, and regional thrusting directions determined from fault-related folds and slickenlines. This study shows that fault population analysis in syntectonic strata provides an opportunity to constrain kinematic evolution during orogeny.     

Geochronological and geochemical constraints on the genesis of the Tieshan complex in the Edong district,Eastern China with implications for Fe and Cu skarn mineralization

Fe and Cu skarn deposits constitute the most important skarn type worldwide, whereas the controlling factors that lead to the difference in metal associations remain not well known. The Fe- and Cu-hosting Tieshan complex in the Edong district provides a good opportunity for comparative study on the genetic differences between Fe and Cu skarn deposits. In this study, integrated studies of geochronology, geochemistry and Sr-Nd-Hf isotope compositions were conducted on the complex. LA-ICP-MS zircon U-Pb dating results show that the Tieshan complex was emplaced in the time interval of 135 ± 3 to 144 ± 1 Ma. Multiphase rocks from the complex can be broadly subdivided into two suites. The Fe-Cu-related suite, which consists of diopside diorite, quartz diorite, quartz diorite porphyrite and porphyritic granodiorite, possesses low SiO₂ (53.5–67.1 wt.%), K₂O (2.44–3.53 wt.%) and Rb (45−83 ppm) contents, but high Sr (1132−2684 ppm), Ba (1073−1656 ppm) contents and negligible Eu anomalies, with very high Sr/Y (>90) ratios, similar to typical high Ba-Sr granitoids. The rock suite has initial ⁸⁷Sr/⁸⁶Sr values of 0.70648 to 0.70737, ε_Nd(t) values of −12.3 to −8.2 and ε_Hf(t) values of −16 to −7, comparable to values of the Early Cretaceous mafic rocks in the Edong district and adjacent areas, indicating that it might be largely derived from an enriched lithospheric mantle source, along with minor involvement of lower-crustal components. By contrast, the Fe-related suite, which is composed of quartz diorite, quartz diorite porphyrite and granodiorite porphyry, is characterized by relatively high SiO₂ (63.0–71.0 wt.%) and K₂O contents (3.36–5.53 wt.%), and a wide range of Sr (158−1135 ppm), Ba (762−1366 ppm) contents and Sr/Y (11–99) ratios. In combination with the presence of abundant inherited zircon grains, the lower ε_Nd(t) (−12.4 to −9.3) and ε_Hf(t) (−25 to −15) values indicate a greater degree of lower-crustal contribution for the Fe-related suite. In addition, the calculated zircon Ce (Ce/Ce* and Ce⁴⁺/Ce³⁺) and Eu (Eu/Eu*) anomalies suggest that the Fe-Cu-related suite has much higher oxygen fugacity (fO₂) than the Fe-related suite. This study highlights fO₂ and fractionation degree of magma as useful indicators for differentiating Fe and Cu skarn mineralization.     

Effect of overburden pressure and degree of saturation on compressibility characteristics

The settlement of a structure founded on clay comprises of immediate and consolidation settlements. In the case of clays, consolidation settlement is more than immediate settlement. The parameters influencing consolidation settlement of a normally loaded clay layer are degree of saturation (S%), void ratio (e) of soil prior to excavation, amount of overburden (σ_o) removed, amount of rebound and intensity of loading (σ) upon building superstructure. This paper presents the effect of the above parameters on compressibility characteristics of a clay. The different steps undertaken for footing construction were simulated in the laboratory. Remoulded clay samples were prepared from oven-dry fraction passing 425 μm sieve. The density of the samples was kept constant at 13 kN/m³. Degree of saturation was varied at 25%, 50%, 75% and 100%. The surcharge on the samples (overburden in the case of field clay layer) was varied as 25 kPa, 50 kPa and 100 kPa. Compressibility characteristics such as initial compression under the applied surcharge (overburden), rebound upon removal of surcharge and recompression were studied through one-dimensional consolidation tests. The rate and amount of initial compression, rebound, e-σ and e-log σ curves, compression index (C_c), coefficient of compressibility (a_v) and coefficient of volume compressibility (m_v) were studied.     

High temperature calorimetry of sulfide systems. I. Thermochemistry of liquid and solid phases of Ni + S

An experimental arrangement suitable for application of high temperature calorimetry to liquid sulfide systems has been developed. Using this approach, we have measured the integral enthalpies of mixing of Ni + NiS at 1100 K to form liquid alloys with compositions from X_Nis = 0.576 to X_Nis = 0.754. Partial enthalpies of the two components also were measured. After correcting for the enthalpies of fusion of Ni and NiS at 1100 K, the results of all measurements can be represented by an analytical expression which reflects subregular behavior of the mixing enthalpies ΔH_mix^l−1 = X_Nis²X_NiA + X_NisX_NiS²B with A = −97.712 kJ mol⁻¹ and B = −4.772 kJ mol⁻¹.The standard enthalpies of formation of the high and low temperature forms of NiS were evaluated from the calorimetrically measured enthalpy change associated with the reaction between nickel and sulfur at 1021 K. The standard enthalpies of formation of Ni₃S₂ (heazlewoodite), Ni₇S₆ and Ni_0.958S were determined from the enthalpy changes of reactions in which the compounds were formed from NiS and Ni at 873 K and 833 K. The standard enthalpy of formation of NiS₂(vaesite) was obtained from the enthalpy change of the reaction of NiS₂ with Ni to give NiS at 873 K. The following values are reported for the standard enthalpies of formation of the phases studied (in kJ mol⁻¹): ΔH_f,NiS(HT)⁰ = −88.1 ± 1.0 ΔH_{f, Ni0.958S}⁰ = −93.2 ± 0.7ΔH_f,Ni7S6⁰ = −582.8 ± 5.7 ΔH_f,NiS(LT)⁰ = −91.0 ± 1.0ΔH_f,Ni3S2(LT)⁰ = −217.2 ± 1.6 ΔH_f,NiS2⁰ = −124.9 ± 1.0.