An experimental and theoretical determination of oxygen isotope fractionation in the system magnetite-H2O from 300 to 800°C

Oxygen isotope fractionations have been determined between magnetite and water from 300 to 800°C and pressures between 10 and 215MPa. We selected three reaction pathways to investigate fractionation: (a) reaction of fine-grained magnetite with dilute aqueous NaCl solutions; (b) reduction of fine-grained hematite through reaction with dilute acetic acid; and (c) oxidation of fine iron power in either pure water or dilute NaCl solutions. Effective use of acetic acid was limited to temperatures up to about 400°C, whereas oxide-solution isotope exchange experiments were conducted at all temperatures. Equilibrium ¹⁸O/¹⁶O fractionation factors were calculated from the oxide-water experiments by means of the partial isotope exchange method, where generally four isotopically different waters were used at any given temperature. Each run product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and on a limited basis, high-resolution transmission electron microscopy (HRTEM) and Mössbauer spectroscopy. Results from the microscopic examinations indicate the formation of well-crystallized octahedra and dodecahedra of magnetite where the extent of crystallization, grain size, and grain habit depend on the initial starting material, P, T, solution composition, and duration of the run.The greatest amount of oxygen isotope exchange (∼90% or greater) was observed in experiments where magnetite either recrystallized in the presence of 0.5 m NaCl from 500 to 800°C or formed from hematite reacted with 0.5 m acetic acid at 300, 350 and 400°C. Fractionation factors (10³ ln α_mt-H2O) determined from these partial exchange experiments exhibit a steep decrease (to more negative values) with decreasing temperature down to about 500°C, followed by shallower slope. A least-squares regression model of these partial exchange data, which accounts for analytical errors and errors generated by mass balance calculations, gives the following expression for fractionation that exhibits no minimum: 1000lnα_lmt-lw=−8.984(±0.3803)x+3.302(±0.377)x²—0.426(±0.092)x³ with an R² = 0.99 for 300 ≤ T≤ 800°C (x = 10⁶/T²). The Fe oxidation results also exhibit this type of temperature dependence but shifted to slightly more negative 10³ ln α values; there is the suggestion that a kinetic isotope effect may contribute to these fractionations. A theoretical assessment of oxygen isotope fractionation using β-factors derived from heat capacity and Mössbauer temperature (second-order Doppler) shift measurements combined with known β-factors for pure water yield fractionations that are somewhat more negative compared to those determined experimentally. This deviation may be due to the combined solute effects of dissolved magnetite plus NaCl (aq), as well as an underestimation of β_mt at low temperatures. The new magnetite-water experimental fractionations agree reasonably well with results reported from other experimental studies for temperatures ≥ 500°C, but differ significantly with estimates based on quasi-theoretical and empirical approaches. Calcite-magnetite and quartz-magnetite fractionation factors estimated from the combination of magnetite β’s calculated in this study with those for calcite and quartz reported by Clayton and Kieffer (1991) agree very closely with experimentally determined mineral-pair fractionations.     

Geochemical evidence for abrupt changes in relative strength of the Arabian monsoons during a stadial/interstadial climate transition

The occurrence and propagation of abrupt climate change between the high and low-latitudes has become an important focus of paleoclimatic and paleoceanographic research. The causes of abrupt change have significant implications for understanding future manifestations of similar forcings under late Holocene (‘Anthropocene’) boundary conditions. Of particular interest are signals indicative of sub-millennial scale climate change in the sub-tropics of similar magnitude and frequency to those recorded in Greenland ice cores. Earlier research in the Arabian Sea has highlighted the sensitivity of sedimentary organic carbon and nitrogen isotope measurements for recording the state of the SW monsoon and associated Arabian Sea Oxygen Minimum Zone. In this study, we exploit the unprecedented fidelity of the sedimentary δ¹⁵N record to identify a 20 cm interval at ODP Site 723 containing a stadial/inter-stadial interval between 43-42 Kyr BP. We employ sedimentary nitrogen isotopes, chlorin pigment and alkenone abundances, major and minor element analyses of highly-resolved (2 mm ≈ 10 yr) samples across this interval to compare a comprehensive, multi-proxy data set to understand (a) the processes contributing to the δ¹⁵N signal in the longer records of denitrification; and (b) the associated climatic events, especially the relative intensity of summer and winter monsoons at these times. A lack of evidence for bioturbation in excess of our 2 mm sampling resolution facilitates decadal-scale oceanographic and climatic reconstructions. Using a four-component flux-dilution model, we show that the deposition of carbonate decreased in parallel with an increase in Total Organic Matter flux from stadial to inter-stadial time. This interval is also marked by a significant drop in lithogenic (dust) accumulation, analogous to a similar decrease noted during deglaciation in the Western Arabian Sea. Combined with alkenone U₃₇^K′-derived estimates for sea surface temperature (SST), we conclude that the climatological shift from stadial to inter-stadial conditions at low latitudes was characterized by repeated switches in mean monsoon state approximately every 200 yr. The winter monsoon was the dominant mode during maximum stadial conditions; conversely the summer monsoon was dominant during maximum interstadial-like conditions. However, each interval was separated by a distinct ‘inter-monsoon’ mode, indicated by a higher continental dust flux but warmer SST. Proxy records for changing bottom-water oxygenation show near-identical results down to the mm-scale, but hint at increased export production leading the onset of anoxia during the stadial/inter-stadial transition. The coherence of all sedimentary signals depicts a wholesale reorganization of the Arabian Sea climate and marine ecosystem over approximately 200 years, a period that may be associated with monsoon modulation by small oscillations in solar irradiance.     

Soil moisture potential and water content in the unsaturated zone within the arid Ejina Oasis in Northwest China

Three soil profiles were selected in the Ejina Oasis, northwest China, to determine water content profiles and evolution of soil moisture potentials in the unsaturated zone within the arid area. The total soil moisture potentials have been monitored for about 3 months in 2001 at different depths in the soil profiles. The occurrence and movement of water in the unsaturated zone was analyzed using the zero flux plane (ZFP) method. It is shown that convergent ZFPs and divergent ZFPs may occur at depths between 0.5 and 3.0 m, and that the depth of the ZFPs was controlled by the root zone of plants growing on the land surface. Profiles of the total soil moisture potentials were observed to be coincident with those of the water contents at the three experimental sites. The total soil moisture potential showed a slight increasing trend and the ZFPs tend to vanish from summer to winter as the water extraction by roots decreased. Evapotranspiration through vegetation has an important bearing on the water content and the total potential in the unsaturated zone.     

Inferring the mass fraction of floc-deposited mud: application to fine-grained turbidites

Fine sediment deposition in the ocean is complicated by the cohesive nature of muds and their tendency to flocculate. The result is disaggregated inorganic grain size (DIGS) distributions of bottom sediment that are influenced by single‐grain and floc deposition. This study outlines a parametric model that characterizes bottom sediment DIGS distributions. Modelled parameters are then used to infer depositional conditions that account for the regional variation in the grain sizes deposited by turbidity currents on the Laurentian Fan–Sohm Abyssal Plain, offshore south‐eastern Canada. Results indicate that, on the channellized Laurentian Fan, the mass fraction of floc‐deposited mud increases only slightly downslope. The small evolution in this fraction arises because sediment concentration and turbulent energy are associated in turbidity currents. On the Sohm Abyssal Plain, however, the mass fraction of floc‐deposited mud decreases, probably as a result of lower sediment concentration at this source‐distal site. Estimates of the mass fraction of mud deposited as flocs suggest that floc deposition is the dominant mode by which sediment is lost from suspension, although single‐grain deposition contributes more to the depositional flux in proximal areas where high energy breaks flocs and in distal areas where low sediment concentration limits floc formation. It is concluded that, throughout the dispersal system, changes in the fraction of flocculated mud deposited from turbidity currents reflect changes in sediment concentration and energy downslope.     

Are isolated stable rigid clasts in shear zones equivalent to voids?

Particles in shear enclose important information about a rock's past and can potentially be used to decipher the kinematic history and mechanical behavior of a certain outcrop or region. Isolated rigid clasts in shear zones often exhibit systematic inclinations with respect to the shear-plane at small angles, tending towards the instantaneous stretching direction of the shear zone. This shape preferred orientation cannot be easily explained by any of the analytical theories used in geology. It was recently recognized that a weak mantle surrounding the clast or a slipping clast–matrix interface might be responsible for the development of the observed inclinations. Physical considerations lead us to conjecture that such mantled, rigid clasts can be effectively treated as voids that are not allowed to change their shape. The resulting equivalent void conjecture agrees well with numerical and field data and has the following important geological implications. (i) Clasts in shear zones can have stable positions in simple shear without the requirement of an additional pure shear component. (ii) The stable orientation can be approached either syn- or antithetically; hence, the clast can rotate against the applied shear sense. (iii) The strain needed to develop a strong shape preferred orientation is small (γ≈1) and therefore evaluations based on other theories may overestimate strain by orders of magnitude. (iv) The reconstruction of far-field shear flow conditions and kinematic vorticity analysis must be modified to incorporate these new findings.     

Middle Campanian–lowermost Maastrichtian nannofossil and foraminiferal biostratigraphy of the northwestern Australian margin

The middle–late Campanian was marked by an increase in the bioprovinciality of calcareous microfossil assemblages into distinct Tethyan, Transitional, and Austral Provinces that persisted to the end of the Maastrichtian. The northwestern Australian margin belonged to the Transitional Province and the absence of key Tethyan marker species such as Radotruncana calcarata and Gansserina gansseri has led petroleum companies operating in the area to use the locally developed KCCM integrated calcareous microfossil zonation scheme. The KCCM zonation is a composite scheme comprising calcareous nannofossil (KCN), planktonic foraminiferal (KPF) and benthonic foraminiferal (KBF) zones. This paper presents the definitions and revisions of Zones KCCM8–19, from the highest occurrence (HO) of Aspidolithus parcus constrictus to the lowest occurrence (LO) of Ceratolithoides aculeus, and builds on our previous early–late Maastrichtian study. The presence of a middle–upper Campanian disconformity is confirmed by microfossil evidence from the Vulcan Sub-basin, Exmouth and Wombat plateaus, and the Southern Carnarvon Platform. In the Vulcan Sub-basin and on the Exmouth Plateau (ODP Hole 762C) the hiatus extends from slightly above the LO of common Rugoglobigerina rugosa to above the LO of Quadrum gothicum. On the Wombat Plateau (ODP Hole 761B) it spans from above the LO of Heterohelix semicostata to above the LO of Quadrum gothicum; and in the Southern Carnarvon Platform the disconformity has its longest duration from above the HO of Heterohelix semicostata to above the LO of Quadrum sissinghii. A significant revision of the events which define Zones KCCM18 and 19 was necessary owing to the observation that the LO of Ceratolithoides aculeus occurs below the HOs of Archaeoglobigerina cretacea and Stensioeina granulata incondita and the LO of common Rugoglobigerina rugosa. In the original zonation these events were considered to be coincident.     

The Gondwanan Carboniferous-Permian Boundary Revisited: New Data from Australia and Argentina

The identification and correlation of the Carboniferous-Permian (Gzhelian-Asselian) boundary within the sedimentary sequences of Gondwana has always been a topic of debate. Type latest Carboniferous and earliest Permian marine sequences are characterised by warm tropical faunas and come from the Uralian Region of Russia and Kazakhstan. Faunas include conodonts and fusulinid foraminiferids which are prime tools for correlation. Such faunal groups are absent from most Gondwanan sequences where reliance for correlations must be placed primarily on brachiopods, bivalve molluscs and palynology. The Western Australian marine sequences, with their contained ammonoids, provide a pivotal link for the dating and correlating of Early Permian Gondwanan sequences with those of the type regions and their palynostratigraphical record is essential for trans-Australian correlations and correlations elsewhere throughout Gondwanaland.New data from the fully cored DM Tangorin DDHl bore hole, drilled in the Cranky Corner Basin, New South Wales, Australia, reveals a sequence of descending faunal zones. The stratigraphically highest zone with Eurydesrna cordaturn, encompasses the Late Sakmarian (Sterlitamakian). The middle zone with Torniopsis elongata, Sulciplica c r a m and Trigonotreta tangorini straddles the Sterlitamakian-Tastubian boundary, with the palynomorphs Pseudoreticulatispora pseudoreticulata high in the zone and Granulatisporites confluens low in the zone. An impoverished fauna with Trigonotreta nov., low in the Granulatisporites confluens Zone, is probably of latest Asselian or Tastubian age.Significant new data from Argentina has revealed marine faunas from below the occurrence of Granulatisporites confluens. These are considered to be of Asselian age. Outcrops of the Tupe Formation, with a marine fauna, at La Herradura Creek in the western Paganzo Basin, San Juan Province, are best regarded as being of mid to late Asselian age. The Tupe Fauna has been recognised as the Tivertonia jachalensis-Streptorhynchus inaequiornatus Zone. Previously, this fauna was considered to be of Late Carboniferous or Stephanian age. Three faunal associations are known from the Rio del Peii6n Formation, Rio Blanco Basin, La Rioja Province. The middle assemblage with Tivertonia, Costaturnulus, Kochiproductus and Trigonotreta, appears to correlate well with the Tupe Formation fauna. The lower assemblage, with Streptorhynchus, Etherilosia, Costaturnulus, Trigonotreta and a punctate spiriferid, as well as indeterminate productids, probably of Early Asselian age. The youngest assemblage includes a species ofRhynchopora that is close to Rhynchopora australasica from the latest Asselian-early Tastubian of Western Australia. The marine biostratigraphical data from Argentina has enabled a much greater understanding of the earliest Permian marine faunas to be achieved - a story that is apparently absent from the other cold and cool temperate regions of Gondwana.     

Fitting the Linear Model of Coregionalization by Generalized Least Squares

In geostatistical studies, the fitting of the linear model of coregionalization (LMC) to direct and cross experimental semivariograms is usually performed with a weighted least-squares (WLS) procedure based on the number of pairs of observations at each lag. So far, no study has investigated the efficiency of other least-squares procedures, such as ordinary least squares (OLS), generalized least squares (GLS), and WLS with other weighing functions, in the context of the LMC. In this article, we compare the statistical properties of the sill estimators obtained with eight least-squares procedures for fitting the LMC: OLS, four WLS, and three GLS. The WLS procedures are based on approximations of the variance of semivariogram estimates at each distance lag. The GLS procedures use a variance–covariance matrix of semivariogram estimates that is (i) estimated using the fourth-order moments with sill estimates (GLS₁), (ii) calculated using the fourth-order moments with the theoretical sills (GLS₂), and (iii) based on an approximation using the correlation between semivariogram estimates in the case of spatial independence of the observations (GLS₃). The current algorithm for fitting the LMC by WLS while ensuring the positive semidefiniteness of sill matrix estimates is modified to include any least-squares procedure. A Monte Carlo study is performed for 16 scenarios corresponding to different combinations of the number of variables, number of spatial structures, values of ranges, and scale dependence of the correlations among variables. Simulation results show that the mean square error is accounted for mostly by the variance of the sill estimators instead of their squared bias. Overall, the estimated GLS₁ and theoretical GLS₂ are the most efficient, followed by the WLS procedure that is based on the number of pairs of observations and the average distance at each lag. On that basis, GLS₁ can be recommended for future studies using the LMC.     

Ar–Ar age determinations of eclogitic clinopyroxene and garnet inclusions in diamonds from the Venetia and Orapa kimberlites

Ar–Ar age measurements are reported for selected eclogitic clinopyroxene and garnet inclusions in Orapa diamonds and clinopyroxene inclusions in Venetia diamonds. Laser drilling of encapsulated clinopyroxene inclusions within Venetia diamonds released a maximum of 3% of the total ⁴⁰Ar, indicating little diffusive transfer and storage of radiogenic ⁴⁰Ar at the diamond–inclusion boundary. Apparent ages obtained during stepped heating of three diamonds are consistent with diamond crystallisation occurring just prior to the kimberlite eruption 520 Ma ago. Stepped heating of three clinopyroxene-bearing Orapa diamonds gave ages of 906–1032 Ma, significantly above the eruption age, but consistent with previously determined isotopic ages. A few higher apparent ages hint at the presence an older generation of Orapa diamonds that formed >2500 Ma ago. Orapa garnets also contain measurable K contents, and record a range of ages between 1000 and 2500 Ma. The old apparent ages and lack of significant interface ⁴⁰Ar released by the laser probe, suggests that pre-eruption radiogenic ⁴⁰Ar and mantle-derived ⁴⁰Ar components are trapped in microinclusions within the pyroxene and garnet inclusions.