Discrimination of sand dunes and loess deposits using grain-size analysis in northeastern Iran

Identification and characterization of aeolian deposits in arid environments provide information on mechanisms of loess and sand accumulation. The objectives of this study were to (i) identify the distribution of aeolian deposits, (ii) discriminate loess and sand deposits using granulometric data, and (iii) describe the aeolian deposition in Sarakhs area, northeastern Iran. Particle size distributions of 26 surface samples were determined using a laser grain-size analyzer. Fine sand, very fine sand, and very coarse silt were dominant fractions in studied sediments, and the sum of these fractions ranged from 46.9% in loess deposits to 93.8% in sand dunes. The mean grain size (M _z ) of sand dunes ranged from 3.31 to 3.54 ?, which gradually changed to 4.09 to 5.50 ? in loess deposits. Sorting, skewness, and kurtosis ranged from 0.84 to 1.94 ?, 0.18 to 0.49, and 0.76 to 2.38, respectively. Aeolian deposits in the area resulted in the incorporation of Hariroud River system and Kopeh Dagh Mountains for aeolian particle production and accumulation. Alluvial comminution in Hariroud River is suggested the main mechanism of sand and silt production and flood plain environment the main reservoir of these particles. The mountains of Kopeh Dagh act as a barrier and play a key role for sand and loess accumulation.     

GRAIN-SIZE INDICES, CLASSIFICATION AND ENVIRONMENT

Indices based on Wentworth phi values of Q₁, Md and Q₃ are used for textural classification of sediments. Wentworth phi values enable a detailed subdivision. A nomenclature based on the Wentworth phi indices is developed. The indices, and to a smaller degree the names, show sorting and skewness based on integer phi units. The classification scheme gives a continuous scale from gravel to fine clay. The Q₁MdQ₃-indices can be used for distinction of river, marine and loess deposits. The addition of indices of the 1st and 99th percentile, giving 5-digit indices, augments the possibilities for a determination of the environment: river deposits can be distinguished from beach and dune sediments and in more detail from shallow marine and coastal deposits. The indices can be handled by data-processing machines.     

Sanmenxia Loess and Paleoenvironmental Change

INTRODUCTIONThe Sanmenxia area is located at the SE marginof the Loess Plateau,where a thick-layered loess de-posit developed(Fig.1).Previous research has al-ready been carried out on some loess stratigraphy inthe area(Teng,1988;Xie and Jiang,1987;Yue,1985,1984),which concentrated on petrostratigra-phy and magnetostratigraphy.Further environmentalinvestigation has not yet been pursued.After the ge-ological survey(Zheng et al.,1992;An et al.,1989;Ding and Liu,1989),more integrated str…     

Draa Sfar, Morocco: A Visean (331 Ma) pyrrhotite-rich, polymetallic volcanogenic massive sulphide deposit in a Hercynian sediment-dominant terrane

Draa Sfar is a Visean, stratabound, volcanogenic massive sulphide ore deposit hosted by a Hercynian carbonaceous, black shale-rich succession of the Jebilet terrane, Morocco. The ore deposit contains 10 Mt grading 5.3 wt.% Zn, 2 wt.% Pb, and 0.3 wt.% Cu within two main massive sulphides orebodies, Tazakourt (Zn-rich) and Sidi M'Barek (Zn–Cu rich). Pyrrhotite is by far the dominant sulphide (70 to 95% of total sulphides), sphalerite is fairly abundant, chalcopyrite and galena are accessory, pyrite, arsenopyrite and bismuth minerals are rare. Pyrrhotite is monoclinic and mineralogical criteria indicate that it is of primary origin and not formed during metamorphism. Its composition is very homogeneous, close to Fe₇S₈, and its absolute magnetic susceptibility is 2.10^− 3 SI/g. Ar–Ar dating of hydrothermal sericites from a coherent rhyolite flow or dome within the immediate deposit footwall indicates an age of 331.7 ± 7.9 Ma for the Draa Sfar deposit and rhyolite volcanism.The Draa Sfar deposit has undergone a low-grade regional metamorphic event that caused pervasive recrystallization, followed by a ductile–brittle deformation event that has locally imparted a mylonitic texture to the sulphides and, in part, is responsible for the elongated and sheet-like morphology of the sulphide orebodies. Lead isotope data fall into two compositional end-members. The least radiogenic end-member, (²⁰⁶Pb/²⁰⁴Pb = 18.28), is characteristic of the Tazakourt orebody, whereas the more radiogenic end-member (²⁰⁶Pb/²⁰⁴Pb  18.80) is associated with the Sidi M'Barek orebody, giving a mixing trend between the two end-members. Lead isotope compositions at Draa Sfar testify to a significant continental crust source for the base metals, but are different than those of the Hajar and South Iberian Pyrite Belt VMS deposits.The abundance of pyrrhotite versus pyrite in the orebodies is attributed to low fO₂ conditions and neither a high temperature nor a low aH₂S (below 10^− 3) is required. The highly anoxic conditions required to stabilize pyrrhotite over pyrite are consistent with formation of the deposit within a restricted, sediment-starved, anoxic basin characterized by the deposition of carbonaceous, pelagic sediments along the flank of a rhyolitic flow-dome complex that was buried by pelitic sediments. Deposition of sulphides likely occurred at and below the seafloor within anoxic and carbonaceous muds.Draa Sfar and other Moroccan volcanogenic massive sulphide deposits occur in an epicontinental volcanic domain within the outer zone of the Hercynian belt and formed within a sedimentary environment that has a high pelagic component. In spite of the diachronous emplacement between the IPB deposits (late Devonian to Visean) and Moroccan deposits (Dinantian), all were formed around 340 ± 10 Ma following a major phase of the Devonian compression.     

Geochemical Characteristics of Eolian Deposits on the Eastern Margin of the Tibetan Plateau and Implications for Provenance

Eolian dust deposition is intimately related to atmospheric circulation and environmental setting of the source region, and therefore is an invaluable tool for studying the evolutionary history of atmospheric circulation patterns and paleoclimatic change. Identifying the provenance of any eolian deposit is crucial not only for reconstructing the paleoenvironmental history of the dust source region, but also for understanding the paleoclimatic significance of various indices. Loess and paleosol samples from the Garze region on the eastern margin of the Tibetan Plateau(TP) were analyzed for their elemental(major and trace elements) and isotopic(Sm-Nd) geochemistry and compared with those of Northern Chinese(NC) loess formed at the same age. The results show that the geochemical compositions of the Garze loess and paleosol samples are similar to those eolian deposits on the Chinese Loess Plateau(CLP), and also resemble the average UCC. This indicates that the eolian deposits on the eastern margin of the TP were derived from well-mixed sedimentary protoliths that had undergone numerous upper crustal recycling processes, just as with the CLP loess deposits. However, compared with NC loess, the Garze samples have higher ∑REE, Li, Rb, Zr, Cs, Hf and Bi concentrations, higher TiO2/Al2O3, Hf/Nb, La/Nb, Th/Nb and lower K2O/TiO2, Zr/Hf, Ba/Rb ratios. From the Sm-Nd isotopic geochemistry, εNd(0) and 147Sm/144Nd values of Garze loess and paleosol samples are clearly lower than the NC loess. The higher Bi, Zr and Hf concentrations are relevant to the widely distributed acid-magmatic rocks in this region, whereas the higher contents of Li, Cs, Rb are attributed to the high background values of the TP. The geochemical characteristics of the Garze loess and paleosol samples further prove that the local glacial and other Quaternary detrital sediments are predominantly the contributors for the eolian deposits on the eastern margin of the TP. Stable element concentrations and their ratios in the Garze loess and paleosol samples formed at different times have relatively greater variation ranges in comparison with the NC loess, indicating that the source regions for eolian deposits have been unstable since the late Early Pleistocene. We attribute the instability of dust sources to variable earth surface conditions and the changeable TP winter monsoon in direction and intensity, which are in turn related to the uplift of the TP.     

郑州邙山桃花峪高分辨率晚更新世黄土地层

风成邙山黄土分布于河南郑州西北黄河南岸。黄土序列较完整,初步研究了桃花峪剖面S₂以上黄土地层,S₀、L₁、S₁、L₂和S₂分别厚0.6m、70.8m、9.9m、12.4m和1.0m。特别有意义的是晚更新世马兰黄土厚度巨大,分辨率高。以10cm间距对邙山桃花峪剖面进行了磁化率测量,并与海洋氧同位素时间序列进行对比,按Kukla等的磁化率年龄模式,获得相应的年代时间标尺。对末次冰期黄土以40cm间距进行了粒度分析,不同冰期或冰阶的平均沉积速率和分辨率有很大的差异。特别是末次冰期晚冰阶黄土粒度所反映的冬季风振荡的频率和幅度都超过了格陵兰冰芯记录。邙山晚更新世黄土地层是进行高分辨率黄土地层与短时间尺度过去全球变化研究的极好对象.      

Mineralogische Beobachtungen an Colemanit,Inyoit, Meyerhofferit,Tertschit und Ulexit aus neuen türkischen Boratlagerstätten

Zusammenfassung Nachdem seit Jahrhunderten um Sultançayir bloß Priceit (Pandermit) gewonnen wurde und weitere Borate aus Westanatolien nicht bekannt waren, sind nun seit 1951 weiter südlich neue Boratlagerstätten mit vorwiegend Colemanit entdeckt worden [9]. Hier erfolgt die mineralogische Bearbeitung eines größeren Materials aus verschiedenen Vorkommen, in derv die im Titel genannten Minerale nachgewiesen werden konnten. Von Colemanit flächenreiche Kristalle in einer neuen Tracht und bemerkenswerte Wachstumsformen und -gefüge. Inyoit- und Meyerhofferit-Kristalle, letztere u. a. mit 2 neuen Fldchen. Pseudomorphosen von Colemanit nach Inyoit und von Kalkspat nach Colemanit und Meyerhofferit. Beobachtungen an Ulexit und Tertschit. Einige Pulver (d _hkl )-Daten für Kalkborate, kurze Angaben über das Lumineszenzverhalten. Der Tonschiefer, in dem die Borate lagern, dürfte als Bentonit aufzufassen sein. Die Gesamtparagenese der neuen und alien türkischen Boratlagerstatten ist der Typus Kalifornien [9].[/p]Lagerstättenuntersuchung der Österr. Alpinen Montan-Gesellschaft.     

中原邙山黄土地层

位于黄土高原与华北平原过渡带上的中原黄土地层,以邙山赵下峪剖面为其典型代表。据光释光和热释光测年及磁性地层研究结果,该剖面从邙山塬面至黄河河床出露S₀-S₁₀黄土-古土壤序列,总厚度172.1m,B/M界线记录于S₈古土壤层顶部,以厚层晚更新世S₁古土壤(15.7m)和巨厚L₁黄土(77.3m)为其特色。赵下峪剖面上末次间冰期以来的平均沉积速率明显增大,其中以末次冰期晚冰阶L₁LL₁黄土的沉积速率最大,高达34.5mm/a。在邙山黄土堆积过程中,倒数第二冰期末(相当于L₂顶部),约150ka B P,发生了风尘沉积速率的突变,其原因是此时黄河贯通三门峡东流,给风尘源区带来丰富的物质。同时赵下峪剖面的磁化率曲线所示,黄土-古土壤的磁化率强弱,并不简单地反映夏季风强度,也要受到沉积速率变化的影响。      

Sulphur isotopic investigation of lower carboniferous vein deposits of the British Isles

Similar characteristics and age data suggest that the Pb + Zn vein deposits hosted by Lower Palaeozoic and Vendian strata of the British Isles form a genetically related group, coeval with the Lower Carboniferous carbonatehosted base-metal deposits of Ireland. Sulphur isotopic data demonstrate that there were separate sulphide and sulphate sulphur sources for the vein minerals. ³⁴S values from minerals in individual vein systems are consistent but there is a large variation between deposits, revealing distinctive local sulphur sources. The data suggests that sulphide sulphur (total range of values of ³⁴S_H2S of -6.5 to 18.62) was derived from the underlying strata while the sulphate (baryte) sulphur source (³⁴S_baryte mainly in the range 12 to 24) was groundwater or surface water that mixed with rising hydrothermal fluids in the upper reaches of the veins.     

热液体系氩同位素示踪研究

 采用分阶段加热爆裂法测定了不同成因热液矿床脉石英流体包裹体的氩同位素,计算出各温度段内大气氩的相对含量,从而,总结出大气降水热液矿床、再平衡岩浆水热液矿床等成矿流体的氩同位素组成特征及其演化规律。典型的大气降水热液矿床,其成矿流体以具有高大气Ar组分(约95%-100%)为特征;再平衡岩浆水热液矿床成矿流体的Ar同位素组成特征取决于与其有成因关系的初始岩浆水的Ar同位素组成及矿源层和围岩的性质,产于古老变质岩中的,一般以具有低大气Ar组分(约6%-20%)为特征,其它的再平衡岩浆水热液矿床在主成矿温度范围内一般为50%-60%左右。     

Tonminerale in normalsedimenten,hydrothermal beeinflu\ten sedimenten und Erzschlämmen des Roten Meeres

From 14 deeps and other regions of the Red Sea totally 226 samples from 28 cores recovered during the VALDIVIA cruises (1971, 1972) were investigated according to their clay mineral content (<2μm resp. < 6.3 μm) after carbonate dissolution. Three facies groups are to distinguish:

1. normal sediments: dominance of chlorite, kaolinite, illite, small amounts of smectite and sepiolite. Two palygorskite types are present only in a few samples.
2. normal sediments with hydrothermal influence: clay mineral paragenesis similar like that of normal sediments; but increase of smectite and presence of goethite in each sample; partly small contents of talc.
3. heavy metal deposits: dominance of iron-bearing smectite, partly with amorphous components resp. pure ore mineral assemblages with authigenic silicates (talc, quartz, opal, chrysotile, sepiolite, palygorskite, chlorite).

Crystallinity of the clay and ore minerals is independent from sedimentary overburden. Sepiolite shows in small amounts a wide distribution; palygorskite₂ (d₁₁₀=11.3 Å) yields locally an increased concentration in the range of pteropod layers cemented by aragonite. The environment of ore deposits is characterized by iron-bearing smectite besides the ore minerals.     

Lithogeochemical halos and geochemical vectors to stratiform sediment hosted Zn–Pb–Ag deposits, 1. Lady Loretta Deposit, Queensland

Stratiform sediment hosted Zn–Pb–Ag deposits, often referred to as SEDEX deposits, represent an economically important class of ore, that have received relatively little attention in terms of defining lithochemical halos and geochemical vectors useful to exploration. This study concentrates on the Lady Loretta deposit which is a typical example of the class of Proterozoic SEDEX deposits in northern Australia. We examined the major and trace element chemistry of carbonate-bearing sediments surrounding the deposit and defined a series of halos which extend for several hundred metres across strike and up to 1.5 km along strike. The stratiform ore lens is surrounded by an inner sideritic halo [Carr, G.R., 1984. Primary geochemical and mineralogical dispersion in the vicinity of the Lady Loretta Zn–Pb–Ag deposit, North Queensland. J. Geochem. Expl. 22, 217–238], followed by an outer ankerite/ferroan dolomite halo which merges with low iron dolomitic sediments representative of the regional background compositions. Carbonate within the inner siderite halo varies in composition from siderite to pistomesite (Fe_0.6Mg_0.4CO₃), whereas carbonate in the outer ankerite halo varies from ferroan dolomite to ankerite (Ca_0.5Mg_0.3Fe_0.2CO₃). Element dispersion around the stratiform ore lens is variable with Pb, Cu, Ba and Sr showing very little dispersion (<50 m across strike), Zn and Fe showing moderate dispersion (<100 m) and Mn and Tl showing broad dispersion (<200 m). Within the siderite halo Cu, Mg and Na show marked depletion compared to the surrounding sediments. The magnitude of element dispersion and change in carbonate chemistry around the Lady Loretta orebody has enabled the development of three geochemical vectors applicable to exploration. Whole rock analyses are used to calculate the three vector quantities as follows: (1) SEDEX metal index = Zn + 100Pb + 100Tl; (2) SEDEX alteration index = (FeO + 10MnO)100/(FeO + 10MnO + MgO); (3) manganese content of dolomite: MnO_d = (MnO × 30.41)/CaO. All three vectors increase to ore both across strike and along strike. The manganese content of dolomite (MnO_d) exhibits the most systematic pattern increasing from background values of about 0.2 wt% to a maximum of around 0.6 wt% at the boundary between the ankerite and siderite halos. Siderite within the inner halo contains considerably more Mn with MnO values of 0.4 to 4.0 wt%. It is suggested here that the basket of indices defined at Lady Loretta (Zn, Tl, metal index, alteration index, MnO_d and MnO_s) is applicable in the exploration for stratiform Zn–Pb–Ag deposits in dolomite-rich sedimentary basins generally. The indices defined can firstly assist in the identification of sedimentary units favourable for SEDEX mineralisation, and secondly provide vectors along these units to ore. The alteration index and MnO_d, however, should only be used for exploration dolomitic sequences; they are not recommended for exploration in clastic sequences devoid of carbonates.     

Evidence for Holocene Aeolian Activity at the Close of the Middle Bronze Age in the Eastern Carpathian Basin: Geoarchaeological Results from the Mureş River Valley,Romania

While extensive Pleistocene loess deposits have been identified across Eurasia, Holocene age loess (typically nonglaciogenic) is rarely recognized. We explore possible loess deposits in the Mureş River Valley of western Romania, providing a regional signal of increased aridity during the mid‐late Holocene. This proposed aridity may be responsible for the abandonment of Middle Bronze Age tell settlements along the major drainages of the eastern Carpathian Basin (Pannonian plain). This hypothesis centers on a proposed aeolian deposit (the “Pecica deposit”), a ca. 50–80 cm thick, relatively homogeneous, gray layer blanketing the top of the Bronze Age tell of Pecica—Şanţul Mare. Comparing the morphological, geochemical, and physical characteristics of this specific tell deposit with two representative profiles near the site containing glaciogenic calcareous loess and potential Holocene loess deposits developed in Chernozems, we find significant similarities to support this hypothesis. We then review various forms of proxy data published from elsewhere in Central and Eastern Europe suggesting a warming trend during this period. The temporal placement of the Pecica deposit is bracketed using diagnostic artifacts, radiocarbon dates, and the degree of soil development, suggesting a period of increased aridity likely occurring soon after the 17th century B.C.     

Fe-Zn exchange reaction between tetrahedrite and sphalerite in natural environments

Microprobe and fluid inclusion analyses of hydrothermal ore deposits containing the subassemblage sphalerite+ tetrahedrite-tennantite [(Cu, Ag)₁₀(Fe, Zn)₂(As,Sb)₄S₁₃] reveal that the Gibbs energies of the reciprocal reaction Cu₁₀Zn₂Sb₄S₁₃ + Cu₁₀Fe₂As₄S₁₃ = Cu₁₀Fe₂Sb₄S₁₃ + Cu₁₀Zn₂As₄S₁₃ and the Fe-Zn exchange reaction 1/2Cu₁₀Fe₂Sb₄S₁₃ + ZnS = 1/2Cu₁₀Zn₂Sb₄S₁₃ + FeS are within the uncertainties of the values established by Sack and Loucks (1985) and Raabe and Sack (1984), 2.59±0.14 and 2.07±0.07 kcal/gfw. However, this study suggests that the Fe-Zn exchange reaction between sphalerite and Sb and Ag-rich tetrahedrites does not obey the simple systematics suggested by Sack and Loucks (1985) wherein tetrahedrite is assumed to behave as an ideal reciprocal solution. Instead these studies show that the configurational Gibbs energy of this exchange reaction,RTln[(X _Fe/X _Zn)^TET(X _ZnS/X _FeS)^SPH], corrected for sphalerite nonideality exhibits both a local maximum and minimum as a function of Ag/(Cu+Ag) ratio at a givenX _FeS ^SPH and temperature. The local maximum forX _FeS ^SPH 0.10 corresponds to the position of the cell edge maximum established for natural tetrahedrites by Riley (1974), Ag/(Ag+Cu)0.4. These studies and the results of structural refinements of Ag-bearing tetrahedrites suggest that in low silver tetrahedrites Ag is preferentially incorporated in trigonal-planar sites but that in tetrahedrites with intermediate and greater Ag/(Ag+Cu) ratio, Ag is preferentially incorporated in tetrahedral sites. A nonconvergent site ordering model for tetrahedrite is developed to quantify and extrapolate these predictions.     

Violan revisited: Mn-bearing omphacite and diopside

Summary Violet clinopyroxenes (violan) from the manganese deposit of Praborna, near St. Marcel (Aosta Valley, Italy) occur in two different varieties: euhedral crystals grown in vugs and massive lamellar to fibrous aggregates. The euhedral crystals are predominantlyP2/n omphacite with a(Di+Hd+Jo)/(Jd+Ac+Mnjd) ratio close to unity. The lamellar aggregates consist mainly of disorderedC2/c impure diopside with alternating patches of pure diopsidic and moderately omphacitic compositions.The deep violet colour, occasionally shading to blue, is presumably due to the presence of both Mn³⁺ and Mn²⁺ ions. Detailed crystal structure determinations andEPR spectra investigations, however, did not clearly solve the question of the oxidation state of manganese because of the low amounts of manganese being present in violan. Crystal structure determinations and microprobe analyses nevertheless clearly showed that violan is not a mineral species. The name should therefore be reserved for the ex-colore violet varieties of both diopside and omphacite.

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Violan, ein Mn-führender Omphacit und Diopsid

Zusammenfassung Violett gefärbte Klinopyroxene (violan) von der Manganlagerstätte Praborna bei St. Marcel (Aosta-Tal, Italien) bilden entweder idiomorphe Kristalle in Hohlräumen, oder massive lamellare bis feinfaserige Aggregate. Die idiomorphen Kristalle sind zum überwiegenden TeilP2/n Omphazite mit einem (Di+Hd+Jo):(Jd+Ac+Mnjd) Verhältnis von etwa 1 1. Die lamellaren Aggregate bestehen hauptsächlich aus ungeordnetemC2/c Diopsid, wobei die chemische Zusammesetzung partienweise zwischen diopsidisch und leicht omphazitisch wechselt.Die tief violette Farbe wird wahrscheinlich durch das Vorhandensein von Mn³⁺ und Mn²⁺-Ionen verursacht. Eine eindeutige Klärung dieser Frage war jedoch trotz detaillierter Kristallstruktur-Bestimmung und Auswertung vonEPR Spektren nicht möglich, da der Mangangehalt der Violane überraschend gering ist.Die detaillierten Kristallstruktur-Analysen ergaben jedoch eindeutig, daß Violan keine selbständige Mineralspecies ist. Dieser Name sollte daher nur für die violetten Farbvarietäten von Omphaziten und Diopsiden verwendet werden.

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The rare earth element compositions of sediments from the loess tableland in the Liyang Plain,southern China: implications for provenance and weathering intensity

To identify the weathering intensity and to deduce the provenance of sediments (black-brown soil and loess) from the loess tableland in the Liyang Plain is of great importance for understanding the development and origin of civilization of this critical region in China. The geochemical results show similar REE distribution patterns among sediments sampled from the YC profile in the Liyang Plain, reticulated red soils from the Dongting lake area, Xiashu loess in Zhenjiang, and loess from the Loess Plateau in China. These similarities imply a single provenance, from dust storms. REEs, especially the LREE/HREE ratio and Eu anomaly, can trace weathering intensity. Higher LREE/HREE ratios, and remarkably Eu anomalies, are present in the top loess (L₀), Lower LREE/HREE ratios and insignificant Eu anomalies are present in black-brown soil (S₀*) from the Liyang Plain. These demonstrate that the black-brown soils have undergone a lower intensity of weathering than the loess of YC profile. Moreover, CIA values for sediments from the YC profile provide powerful evidence to support the above result. Comparisons of analyses of the REE contents of sediments from the YC profile, of reticulated red soils from the Dongting Lake area, Xiashu loess from the Yangtze River, and loess from the Loess Plateau, clearly show the weathering intensity decreases according to the following sequence: reticulated red soil from the Dongting Lake area > sediments of YC profile from the Liyang Plain, which formed from dust storms ≈ Xiashu loess from lower reach of the Yangtze River > loess from the Loess Plateau.     

Thermodynamic data from redox reactions at high temperatures. III. Activity-composition relations in Ni-Pd alloys from EMF measurements at 850–1250 K,and calibration of the NiO+Ni-Pd assemblage as a redox sensor

The assemblage NiO+Ni-Pd alloy has been calibrated as a precise oxygen fugacity sensor in the temperature range 850–1250 K at 1 bar, using an electrochemical technique with oxygen-specific CSZ electrolytes, and Ni+NiO and Cu+Cu₂O as the reference electrodes. Nine compositions were studied, ranging from 0.12 to 0.83 X _Ni ^alloy . Steady EMFs, implying equilibrium, were rapidly achieved in all cells, and were found to be reversible on increasing and decreasing temperature with a precision approaching 0.1 mV. The estimated accuracy of the measurements on each cell is ±0.2 mV (1, corresponding to ±0.003 log-bar units in fo₂ at 1273 K). Compositions of the Ni-Pd alloys were measured after each run by electron microprobe, and these compositions were then checked for internal consistency by measuring the lattice parameter by X-ray diffraction. Nickel-rich alloys show positive deviations from ideality and endothermic enthalpies of mixing, but palladium-rich compositions have exothermic enthalpies of mixing and strong negative deviations from ideality. The excess entropies of mixing are positive for all compositions, and correlate approximately with the excess volumes of mixing. The highly asymmetrical deviations from ideality are well described by a polynomial expression of the Redlich-Kister form, with three terms for the enthalpies, and two for the excess entropies and volumes of mixing. The experimental data from this study have been used to re-formulate the Ni-Pd oxygen fugacity sensor to give an expression; _O2 ^ss = _O2 ^NNO – 2RT ln X _Ni ^alloy – [2 · (1 – X _Ni ^alloy )² · [(–2165–7.958 · T) + (9409 – 0.888 · T) · (4 X _Ni ^alloy – 1) + 2089 · (6 X _Ni ^alloy – 1) · (2 X _Ni ^alloy – 1)]](850<T<1300) where _O2 ^ss is in J mol^-1, T is in kelvins, and the expression for _O2 ^NNO is that given by O'Neill and Pownceby (1993). Values in terms of log fo₂ may be obtained from the above by dividing by RT ln 10. The estimated standard error in _O2 ^ss is on the order of ±200 J mol^-1, which is approximately ±0.01 log-bar units in fo₂ at 1273 K.     

Co2+ in trigonal fields of oxygen based structures: Electronic absorption spectra of buetschliite-type K2Co(SeO3)2, K2Co2(SeO3)3 and zemannite-type K2Co2(SeO3)3 · 2H2O

Polarized single crystal absorption spectra, in the spectral range 40 000–5 000 cm^-1, were obtained on Co²⁺ in trigonally distorted octahedral oxygen fields of buetschliite-type K₂Co(SeO₃)₂ (I), K₂Co₂(SeO₃)₃ (II) and zemannite-type K₂Co₂(SeO₃)₃ · 2H₂O (III). Site symmetries of Co²⁺ are m (D_3d) in I, 3m (C_3v) in II, and 3 (C₃) in III. The spectra can be interpreted on the basis of an electric dipole mechanism, wherein transitions of Co²⁺ in the centrosymmetric site in I gain intensity from dynamic removal of the inversion centre by vibronic coupling. In accordance with the elongation of the CoO₆ octahedra along the trigonal axis, the split component E_(g) of the ground state ⁴T_1g in octahedral fields is the ground state in all three compounds. Trigonal field parameters Dq_(trig), D, D and the Racah parameters B have been fitted to the energies of spin allowed transitions (293 K) as follows: I: 744, 94, -16, and 838 cm^-1, resp.; II: 647, 227, 42, and 798 cm^-1, resp.; III: 667, 181, 21, and 809 cm^-1, respectively. Racah parameters C were estimated from the energy of some observed spin-forbidden transitions to be 3770 (I), 3280 (II), and 3465 cm^-1 (III). Values of Dq and of the Racah parameters B and C indicate slight differences of Co²⁺-O bonding in I as compared to II and III, with somewhat higher covalency in compounds II and III which contain face-sharing CoO₆ octahedra with short Co-Co contacts. Also, in II and III the observed D values do not agree with theoretical D values, predicted from the magnitude of the mean octahedral distortions.     

The role of iron in tetrahedrite and tennantite determined by Rietveld refinement of neutron powder diffraction data

Rietveld refinement of neutron powder diffraction data on four samples of synthetic, iron-bearing tetrahedrite (Cu_12?xFe_xSb₄S₁₃) with x = 0.28, 0.69, 0.91, 2.19 and four samples of synthetic tennantite (Cu_12?xFe_xAs₄S₁₃) with x = 0.33, 0.38, 0.86, 1.5 indicate unambiguously that iron is incorporated into tetrahedral M1 (12d) sites and not into triangular M2 (12e) sites in the cubic crystal structure (space group I $ \ifmmode\expandafter\bar\else\expandafter\=\fi{4} Rietveld refinement of neutron powder diffraction data on four samples of synthetic, iron-bearing tetrahedrite (Cu_12−xFe_xSb₄S₁₃) with x = 0.28, 0.69, 0.91, 2.19 and four samples of synthetic tennantite (Cu_12−xFe_xAs₄S₁₃) with x = 0.33, 0.38, 0.86, 1.5 indicate unambiguously that iron is incorporated into tetrahedral M1 (12d) sites and not into triangular M2 (12e) sites in the cubic crystal structure (space group I 3 m). The refinement results also confirm that M2 is a split (24g), flat-pyramidal site situated statistically on both sides of the S1−S1–S2 triangle. In tetrahedrite, this split is about 0.6 ?, in tennantite about 0.7 ?. Trends in bond lengths and magnitude of the M2 split were evaluated by means of linear regression with Fe concentration as the independent variable.