Isotopic characteristics of precipitation in Slovenia and Croatia: Comparison of continental and maritime stations

The stable isotopic composition of hydrogen and oxygen (δ²H and δ¹⁸O) and tritium activity (³H) were monitored in monthly precipitation at two continental stations (Ljubljana, Zagreb) and six stations along the eastern Adriatic coasts of Slovenia and Croatia in the period 2001–2003. Mean air temperatures and amount of precipitation were also recorded.

Distinct differences in both meteorological and isotopic data between the continental and maritime stations were observed. Seasonal variations in δ¹⁸O are smaller at the maritime stations than at the continental ones due to smaller seasonal temperature variations. A good correlation between δ¹⁸O and δ²H was obtained for each station, and the local meteoric water lines are close to the Global Meteoric Water Line, with a decreasing trend of slope for the south-Adriatic stations. Good correlations between δ¹⁸O in monthly precipitation and mean monthly air temperature were observed at all stations. The slope of δ¹⁸O vs. T varied between 0.37‰ °C⁻¹ and 0.15‰ °C⁻¹. Mean ³H activity and seasonal variation of ³H activity are smaller at maritime stations than at continental ones. Additionally, ³H activity decreases in the NW–SE direction of the Adriatic coast.

The study of spatial variations over this relatively small area rich in geographical and climatic diversities showed the complexity of the isotopic composition of precipitation and the isotopic data obtained for eight stations, most of them in the karstic area along the Adriatic coast, and gave valuable information for regional hydrological investigations and modelling of isotope variability over the Mediterranean basin.     

Silicate perovskite analogue ScAlO3: temperature dependence of elastic moduli

The elastic moduli of ScAlO₃ perovskite, a very close structural analogue for MgSiO₃ perovskite, have been measured between 300 and 600 K using high precision ultrasonic interferometry in an internally heated gas-charged pressure vessel. This new capability for high temperature measurement of elastic wave speeds has been demonstrated on polycrystalline alumina. The temperature derivatives of elastic moduli of Al₂O₃ measured in this study agree within 15% with expectations based on published single-crystal data. For ScAlO₃ perovskite, the value of (∂K_S/∂T)_P is −0.033 GPa K⁻¹ and (∂G/∂T)_P is −0.015 GPa K⁻¹. The relative magnitudes of these derivatives agree with the observation in Duffy and Anderson [Duffy, T.S., Anderson, D.L., 1989. Seismic velocities in mantle minerals and the mineralogy of the upper mantle. J. Geophys. Res. 94, 1895–1912.] that |(∂K_S/∂T)_P| is typically about twice |(∂G/∂T)_P|. The value of (∂K_S/∂T)_P for ScAlO₃ is intermediate between those inferred less directly from V(P,T) studies of Fe-free and Fe- and Al-bearing MgSiO₃ perovskites [Wang, Y., Weidner, D.J., Liebermann, R.C., Zhao, Y., 1994. P–V–T equation of state of (Mg,Fe)SiO₃ perovskite: constraints on composition of the lower mantle. Phys. Earth Planet. Inter. 83, 13–40; Mao, H.K., Hemley, R.J., Shu, J., Chen, L., Jephcoat, A.P., Wu, Y., Bassett, W.A., 1991. Effect of pressure, temperature and composition on the lattice parameters and density of (Mg,Fe) SiO₃ perovskite to 30 GPa. J. Geophys. Res. 91, 8069–8079; Zhang, Weidner, D., 1999. Thermal equation of state of aluminum-enriched silicate perovskite. Science 284, 782–784]. The value of |(∂G/∂T)|_P for ScAlO₃ is similar to those of most other mantle silicate phases but lower than the recent determination for MgSiO₃ perovskite [Sinelnikov, Y., Chen, G., Neuville, D.R., Vaughan, M.T., Liebermann, R.C., 1998. Ultrasonic shear wave velocities of MgSiO₃ perovskite at 8 GPa and 800K and lower mantle composition. Science 281, 677–679].

Combining the results from the previous studies and current measurements on ScAlO₃ perovskite, we extracted the parameters (q and γ₀) needed to fully specify its Mie–Grüneisen–Debye equation-of-state. In this study, we have demonstrated that acoustic measurements of K_S(T), unlike V(P,T) data, tightly constrain the value of q. It is concluded that ScAlO₃ has ‘normal’ γ₀ (1.3) and high q (3.6). The high value of q indicates that ScAlO₃ has very strong intrinsic temperature dependence of the bulk modulus; similar behaviour has been observed in measurements on Fe- and Al-bearing silicate perovskites (Mao et al., 1991; Zhang and Weidner, 1999).     

Correlated chemical and isotopic zoning in carbonates in the martian meteorite ALH84001

The meteorite ALH84001, a sample of the ancient martian crust, contains small quantities (1%) of strongly chemically zoned carbonate. High spatial resolution (10 μm) ion microprobe analyses show that the chemical zoning is strongly correlated with variations in oxygen isotope ratios. Early formed Ca,Fe-rich cores have δ¹⁸O 7‰ increasing to 22‰ SMOW in the more Mg-rich outer cores and magnesite rims. Isolated areas of ankerite appear to be isotopically lighter with δ¹⁸O 1‰. The large range in δ¹⁸O requires a significant range in either fluid isotopic composition, or temperature, or both, in the course of the deposition sequence. Our data are inconsistent with formation of the zoned carbonates by closed system Rayleigh fractionation. There is no unique interpretation of the oxygen data, but the recent observation of existence of Δ¹⁷O excesses in the carbonate appears to rule out models which involve high temperature isotopic exchange with silicate. Comparison with terrestrial analogues suggests that ALH84001 carbonates formed in a hydrothermal system with T<400°C, and which, at least in the early stages of formation, may have involved water with δ¹⁸O < 0‰ SMOW. The later stages of deposition probably occurred at temperatures below 150°C, a conclusion which does not preclude the co-existence of thermophilic bacteria; temperatures during earlier stages of deposition are less likely to have been hospitable to bacteria.     

Glacial–interglacial changes in Subantarctic sea surface temperature and δO-water using foraminiferal Mg

Laboratory culturing experiments with living Globigerina bulloides indicate that Mg/Ca is primarily a function of seawater temperature and suggest that Mg/Ca of fossil specimens is an effective paleotemperature proxy. Using culturing results and a core-top Neogloboquadrina pachyderma calibration, we have estimated glacial–interglacial changes in sea surface temperature (SST) using planktonic Mg/Ca records from core RC11-120 in the Subantarctic Indian Ocean (43°S, 80°E) and core E11-2 in the Subantarctic Pacific Ocean (56°S, 115°W). Our results suggest that glacial SST was about 4°C cooler in the Subantarctic Indian Ocean and 2.5°C cooler in the Subantarctic Pacific. Comparison of SST and planktonic δ¹⁸O records indicates that changes in SST lead changes in δ¹⁸O by on average 1–3 kyr. The glacial–interglacial temperature change indicated by the Subantarctic Mg/Ca records suggests that temperature accounts for 40–60% of the foraminiferal δ¹⁸O change. We have used the Mg/Ca-based SST estimates and δ¹⁸O determinations to generate site-specific seawater δ¹⁸O records, which suggest that seawater δ¹⁸O was on average 1‰ more positive during glacial episodes compared with interglacial episodes.     

Late Pleistocene to Holocene composite speleothem O and C chronologies from South Island, New Zealand—did a global Younger Dryas really exist?

Oxygen and carbon data from eight stalagmites from northwest South Island are combined to produce composite records of δ¹⁸O and δ¹³C from 23.4 ka to the present. The chronology is anchored by 43 thermal ionization mass spectrometry (TIMS) uranium series ages. Delta ¹⁸O values are interpreted as having a first order positive relationship to temperature, but also to be influenced by precipitation in a complex manner. Delta ¹³C is interpreted as responding negatively to increases in atmospheric CO₂ concentration, biological activity and precipitation amount.

Six climatic phases are recognized. After adjustment of 1.2‰ for the ice volume effect, the δ¹⁸O record between 23 and 18 ka varies around −3.72‰ compared to the Holocene average of −3.17‰. Late-glacial warming commenced between 18.2 and 17.8 ka and accelerated after 16.7 ka, culminating in a positive excursion between 14.70 and 13.53 ka. This was followed by a significant negative excursion between 13.53 and 11.14 ka of up to 0.55‰ depth that overlapped the Antarctic Cold Reversal (ACR) and spanned the Younger Dryas (YD). Positive δ¹⁸O excursions at 11.14 ka and 6.91–6.47 ka represent the warmest parts of the Holocene. The mid-Holocene from 6 to 2 ka was marked by negative excursions that coincide with increased glacial activity in the South Island. A short positive excursion from 0.71 to 0.57 ka was slightly later than the Medieval Warm Period of Europe.

Delta ¹³C values were high until 17.79 ka after which there was an abrupt decrease to 17.19 ka followed by a steady decline to a minimum at 10.97 ka. Then followed a general increase, suggesting a drying trend, to 3.23 ka followed by a further general decline. The abrupt decrease in δ-values after 17.79 ka probably corresponds to an increase in atmospheric CO₂ concentration, biological activity and wetness at the end of the Last Glaciation, but the reversal identified in the δ¹⁸O record from 13.53 to 11.14 ka was not reflected in δ¹³C changes. The lowest δ¹³C values coincided with the early Holocene climatic suboptimum when conditions were relatively wet as well as mild.

Major trends in the δ¹⁸O_c record are similar to the Northern Hemisphere, but second order detail is often distinctly different. Consequently, at the millennial scale, a more convincing case can be made for asymmetric climatic response between the two hemispheres rather than synchronicity.     

Response spectra for differential motion of columns paper II: Out-of-plane response

It is shown that the common response spectrum method for synchronous ground motion can be extended to make it applicable for earthquake response analyses of extended structures experiencing differential out-of-plane ground motion. A relative displacement spectrum for design of first-story columns SDC (T, T_T, ζ, ζ_T, τ, δ) is defined. In addition to the natural period of the out-of-plane response, T, and the corresponding fraction of critical damping, ζ, this spectrum also depends on the fundamental period of torsional vibrations, T_T, and the corresponding fraction of critical damping, ζ_T, on the “travel time,” τ (of the waves in the soil over a distance of about one-half the length of the structure), and on a dimensionless factor δ, describing the relative response of the first floor. The new spectrum, SDC, can be estimated by using the empirical scaling equations for relative displacement spectra, SD, and for peak ground velocity, v_max. For recorded strong-motion acceleration, and for symmetric buildings, the new spectrum can be computed from Duhamel's integrals of two uncoupled equations for dynamics equilibrium describing translation and rotation of a two-degree-of-freedom system. This representation is accurate when the energy of the strong-motion is carried by waves in the ground the wavelengths of which are one order of magnitude or more longer than the characteristic length of the structure.     

Fe isotope fractionation in iron meteorites: New insights into metal-sulphide segregation and planetary accretion

Magmatic iron meteorites are considered to be remnants of the metallic cores of differentiated asteroids, and may be used as analogues of planetary core formation. The Fe isotope compositions (δ^57/54Fe) of metal fractions separated from magmatic and non-magmatic iron meteorites span a total range of 0.39‰, with the δ^57/54Fe values of metal fractions separated from the IIAB irons (δ^57/54Fe 0.12 to 0.32‰) being significantly heavier than those from the IIIAB (δ^57/54Fe 0.01 to 0.15‰), IVA (δ^57/54Fe − 0.07 to 0.17‰) and IVB groups (δ^57/54Fe 0.06 to 0.14‰). The δ^57/54Fe values of troilites (FeS) separated from magmatic and non-magmatic irons range from − 0.60 to − 0.12‰, and are isotopically lighter than coexisting metal phases. No systematic relationships exist between metal-sulphide fractionation factor (Δ^57/54Fe_M-FeS = δ^57/54Fe_metal − δ^57/54Fe_FeS) metal composition or meteorite group, however the greatest Δ^57/54Fe_M-FeS values recorded for each group are strikingly similar: 0.79, 0.63, 0.76 and 0.74‰ for the IIAB, IIIAB, IAB and IIICD irons, respectively. Δ^57/54Fe_M-FeS values display a positive correlation with kamacite bandwidth, i.e. the most slowly-cooled meteorites, which should be closest to diffusive equilibrium, have the greatest Δ^57/54Fe_M-FeS values. These observations provide suggestive evidence that Fe isotopic fractionation between metal and troilite is dominated by equilibrium processes and that the maximum Δ^57/54Fe_M-FeS value recorded (0.79 ± 0.09‰) is the best estimate of the equilibrium metal-sulphide Fe isotope fractionation factor. Mass balance models using this fractionation factor in conjunction with metal δ^57/54Fe values and published Fe isotope data for pallasites can explain the relatively heavy δ^57/54Fe values of IIAB metals as a function of large amounts of S in the core of the IIAB parent body, in agreement with published experimental work. However, sequestering of isotopically light Fe into the S-bearing parts of planetary cores cannot explain published differences in the average δ^57/54Fe values of mafic rocks and meteorites derived from the Earth, Moon and Mars and 4-Vesta. The heavy δ^57/54Fe value of the Earth's mantle relative to that of Mars and 4-Vesta may reflect isotopic fractionation due to disproportionation of ferrous iron present in the proto-Earth mantle into isotopically heavy ferric iron hosted in perovskite, which is released into the magma ocean, and isotopically light native iron, which partitions into the core. This process cannot take place at significant levels on smaller planets, such as Mars, as perovskite is only stable at pressures > 23 GPa. Interestingly, the average δ^57/54Fe values of mafic terrestrial and lunar samples are very similar if the High-Ti mare basalts are excluded from the latter. If the Moon's mantle is largely derived from the impactor planet then the isotopically heavy signature of the Moon's mantle requires that the impacting planet also had a mantle with a δ^57/54Fe value heavier than that of Mars or 4-Vesta, which then implies that the impactor planet must have been greater in size than Mars.     

Stable isotope values of Costa Rican surface waters

Stable isotope data of surface waters from the humid tropics in general, and Costa Rica in particular, are scarce. To improve our understanding of the spatial distribution of stable isotopes in surface waters, we measured δ¹⁸O and δD in river and lake (n=63) and precipitation (n=3) samples from Costa Rica. We also present data from the IAEA/WMO isotopes in precipitation network as context for our study. Surface water isotope values do not strongly correlate with elevation, stream head elevation, stream length, distance from Caribbean Sea, or estimated mean annual precipitation for the country as a whole. However, the data show distinct regional trends. The δ¹⁸O and δD values downwind of mountain ranges are inversely related to the altitude of the ranges the air masses traverse. In the lee of the high Talamanca Range, δ¹⁸O values are 6–8‰ lower, while in the lee of the lower Tilarán Range δ¹⁸O values are 2–3‰ lower than upwind sites along the Caribbean Slope. An altitude effect of −1.4‰ δ¹⁸O/km is present on the Pacific slope of southern Costa Rica, equivalent to a temperature effect of −0.3‰/°C. The Nicoya and Osa Peninsulas have higher values than upwind sites, suggesting input of Pacific-sourced moisture, evaporative enrichment, or decreased condensation temperatures. Elevated and increasing d-excess values inland along the Nicaragua Trough suggest a recycled component may be an important contributor to the water budget. These data provide preliminary stable isotope information for Costa Rica, and will benefit paleoclimatic research in the region. More detailed studies would be beneficial to our understanding of the controls on stable isotope composition of tropical waters.     

Open-system degassing of sulfur from Krakatau 1883 magma

We present the first sulfur and oxygen isotopic data for tephra from the catastrophic 1883 eruption of Krakatau. Sulfur isotopic ratios in unaltered Krakatau tephra erupted August 26–27, 1883 are markedly enriched in ³⁴S relative to mantle sulfur. High δ³⁴S values of +6.3 to +16.4‰ can best be explained by open-system or multi-stage degassing of SO₂ from the oxidized rhyodacitic and gray dacitic magmas with ³⁴S enrichment of SO²⁻₄ remaining in the melt. Lower whole-rock δ³⁴S values of +2.6‰ and +4.0‰ in two oxidized gray dacitic samples indicate more primitive subarc mantle sulfur in the 1883 magma chamber. Initial δ³⁴S of the rhyodacitic magma was probably in the +1.5‰ to +4.0‰ range and similar to δ³⁴S values measured in arc volcanic rocks from the Mariana Arc.     

A 53 year seasonally resolved oxygen and carbon isotope record from a modern Gibraltar speleothem: Reconstructed drip water and relationship to local precipitation

The response of a climate proxy against measured temperature, rainfall and atmospheric circulation patterns at sub-annual resolution is the ultimate test of proxy fidelity but very few data exist showing the level of correspondence between speleothem climate proxies and the instrumental climate record. Cave sites on the Gibraltar peninsula provide a unique opportunity to calibrate speleothem climate proxies with the longest known available precipitation isotopes and instrumental records. An actively growing speleothem sampled from New St. Michaels Cave in 2004 is composed of paired laminae consisting of light columnar calcite and a darker microsparitic calcite. Stable isotope analysis of samples micromilled in 100 μm steps at the equivalent of bi-monthly intervals reveals fabric-correlated annual cycles in carbon isotopes, oxygen isotopes and trace elements responding to seasonal changes in cave microclimate, hydrology and ventilation patterns. Calcite δ¹³C values reach a minimum in the light columnar fabric and evidence from trace element behaviour and cave monitoring indicates that this grows under cave ‘winter’ conditions of highest pCO₂, whereas the dark microsparitic calcite, characterised by elevated δ¹³C and δ¹⁸O values grows under low ‘summer’ pCO₂ conditions. Drip water δ¹³C_DIC reaches a minimum in March–April, at which time the attenuated δ¹⁸O signal becomes most representative of winter precipitation. An age model based on cycle counting and the position of the ¹⁴C bomb carbon spike yields a precisely dated winter oxygen isotope proxy of cave seepage water for comparison with the GNIP and instrumental climate record for Gibraltar. The δ¹⁸O characteristics of calcite deposited from drip water representing winter precipitation for each year can be derived from the seasonally resolved record and allows reconstruction of the δ¹⁸O drip water representing winter precipitation for each year from 1951–2004. These data show an encouraging level of correspondence (r² = 0.47) with the δ¹⁸O of rainfall falling each year between October and March and on a decadal scale the δ¹⁸O of reconstructed winter drip water mirrors secular change in mean winter temperatures.     

河套盆地周缘泉水化学组分对2015年4月15日阿左旗MS5.8地震的响应*

根据河套盆地周缘断裂带泉水的氢、氧同位素组成和水化学组分,讨论了该区地下水的化学类型、成因及其与地震活动的关系。于2014年9月下旬和2015年4月15日M_S5.8阿左旗地震震后在河套盆地周缘的乌拉山断裂带、色尔腾断裂带、狼山断裂带以及桌子山断裂带采集了17个泉水和井水样品,测得水样的TDS分布在143.8~42 553.0mg/L范围内,δD和δ¹⁸O值分别在-83.6‰~66.56‰和-11.16‰~8.2‰的范围内,来源为大气降水。根据舒卡列夫分类法,震前水样可划分为13种水化学类型,震后西山咀、圐圙朴隆等5个点采样点泉水的水化学类型发生变化。其中,乌拉山断裂带的水样以HCO₃-Ca型低矿化度地表水为主;色尔腾断裂带、狼山断裂带泉水受白垩系含水层影响,矿化度较高,富含HCO^-₃及SO^2-₄;桌子山一带受煤矿开采影响,水样以富SO^2-₄和Cl^-的高矿化度水为特征。地震前后TDS、阴、阳离子以及γNa/γCl、γ(SO₄+Cl)/γHCO₃、γHCO₃/γCl等毫克当量比值能够较好地反映地震。2015年4月15日阿左旗M_S5.8地震后,呼鲁斯太、迪延阿贵庙及八一井的水化学组成变化较大,对地震响应较为敏感。呼鲁斯太地区泉水的TDS稍有降低,但HCO^-₃在阴离子中所占比例有所增加,表明震后该地区含水层的泉水与较低矿化度的含碳酸盐岩含水层水发生了混合;八一井的TDS值有所增加,γNa/γCl比值有所降低,表明深部高矿化度水的混入;迪延阿贵庙水样的TDS稍有下降,但NaCl的相对含量较震前有所升高,表明有低矿化度NaCl水的混入。本工作不仅确定了该区水文地球化学背景,而且对地震监测和预测具有一定参考价值。     

Helium isotope geochemistry of mid-ocean ridge basalts from the South Atlantic

We report new helium isotope results for 49 basalt glass samples from the Mid-Atlantic Ridge between 1°N and 47°S.³He/⁴He in South Atlantic mid-ocean ridge basalts (MORB) varies between 6.5 and 9.0 R_A (R_A is the atmospheric ratio of1.39 × 10⁻⁶), encompassing the range of previously reported values for MORB erupted away from high³He/⁴He hotspots such as Iceland. He, Sr and Pb isotopes show systematic relationships along the ridge axis. The ridge axis is segmented with respect to geochemical variations, and local spike-like anomalies in³He/⁴He, Pb and Sr isotopes, and trace element ratios such as(La/Sm)_N are prevalent at the latitudes of the islands of St. Helena, Tristan da Cunha and Gough to the east of the ridge. The isotope systematics are consistent with injection beneath the ridge of mantle “blobs” enriched in radiogenic He, Pb and Sr, derived from off-axis hotspot sources. The variability in³He/⁴He along the ridge can be used to refine the hotspot source-migrating-ridge sink model.

MORB from the 2–7°S segment are systematically the least radiogenic samples found along the mid-ocean ridge system to date. Here the depleted mantle source is characterized by⁸⁷Sr/⁸⁶Sr of 0.7022, Pb isotopes close to the geochron and with²⁰⁶Pb/²⁰⁴Pb of 17.7, and³He/⁴He of 8.6–8.9 R_A. The “background contamination” of the subridge mantle, by radiogenic helium derived from off-ridge hotspots, displays a maximum between 20 and 24°S. The HePb and HeSr isotope relations along the ridge indicate that the³He/⁴He ratios are lower for the hotspot sources of St. Helena, Tristan da Cunha and Gough than for the MORB source, consistent with direct measurements of³He/⁴He ratios in the island lavas. Details of the HeSrPb isotope systematics between 12 and 22°S are consistent with early, widespread dispersion of the St. Helena plume into the asthenosphere, probably during flattening of the plume head beneath the thick lithosphere prior to continental breakup. The geographical variation in theHe/Pbratio deduced from the isotope systematics suggests only minor degassing of the plume during this stage. Subsequently, it appears that the plume component reaching the mid-Atlantic ridge was partially outgassed of He during off-ridge hotspot volcanism and related melting activity.

Overall, the similar behavior of He and Pb isotopes along the ridge indicates that the respective mantle sources have evolved under conditions which produced related He and Pb isotope variations.     

Isotope variations in a Sierra Nevada snowpack and their relation to meltwater

Isotopic variations in melting snow are poorly understood. We made weekly measurements at the Central Sierra Snow Laboratory, California, of snow temperature, density, water equivalent and liquid water volume to examine how physical changes within the snowpack govern meltwater δ¹⁸O. Snowpack samples were extracted at 0.1 m intervals from ground level to the top of the snowpack profile between December 1991 and April 1992. Approximately 800 mm of precipitation fell during the study period with δ¹⁸O values between −21.35 and −4.25‰. Corresponding snowpack δ¹⁸O ranged from −22.25 to −6.25‰. The coefficient of variation of δ¹⁸O in snowpack levels decreased from −0.37 to −0.07 from winter to spring, indicating isotopic snowpack homogenization. Meltwater δ¹⁸O ranged from −15.30 to −8.05‰, with variations of up to 2.95‰ observed within a single snowmelt episode, highlighting the need for frequent sampling. Early snowmelt originated in the lower snowpack with higher δ¹⁸O through ground heat flux and rainfall. After the snowpack became isothermal, infiltrating snowmelt displaced the higher δ¹⁸O liquid in the lower snowpack through a piston flow process. Fractionation analysis using a two-component mixing model on the isothermal snowpack indicated that δ¹⁸O in the initial and final half of major snowmelt was 1.30‰ lower and 1.45‰ higher, respectively, than the value from simple mixing. Mean snowpack δ¹⁸O on individual profiling days showed a steady increase from −15.15 to −12.05‰ due to removal of lower δ¹⁸O snowmelt and addition of higher δ¹⁸O rainfall. Results suggest that direct sampling of snowmelt and snow cores should be undertaken to quantify tracer input compositions adequately. The snowmelt sequence also suggests that regimes of early lower δ¹⁸O and later higher δ¹⁸O melt may be modeled and used in catchment tracing studies.     

Low temperature magnetic properties of titanomagnetites

New measurements of high field magnetisation (I_s), remanence (I_s), and coercive force (H_c) are presented between 4 and 300 K for x = 0.4, 0.5, 0.6 and 0.8 (Fe_3−xTi_xO₄). For x = 0.4 a pronounced minimum is found at T100 K and for X = 0.5 and 0.6 broad minima occur around T200 K, apparently coinciding with the temperature for K₁0. The magnetic properties below T60 K ar complex and were found to be significantly changed by cooling in the presence of a high magnetic field. With no applied field during cooling, a distinct decrease in I_s is observed for T60 K, at which temperature there is a peak in the value of I_rs. The effe cooling is to eliminate the sharp decrease in I_s, reduce H_c and to increase I_rs below 60 K to a value the peak value, giving essentially a square hysteresis loop. The results are interpreted in terms of a form of crystallographic phase transition coupled to the magnetisation direction, possibly by the magnetostriction. Square hysteresis loops in ferrites have been explained by the presence of Jahn-Teller ions and, in the present case, the low temperature of the observed effect may be a consequence of the weak Fe²⁺ Jahn-Teller ion coupled to other effects such as spin-lattice coupling.

Details of this work can be found in Schmidbauer, E. and Readman, P.W., 1982. Low temperature magnetic properties of Ti-rich Fe---Ti spinels. J. Magn. Magn. Mat., 27: 114–118. A paper reporting further work on Fe_2.4Ti0.6O0.4 is in preparation.     

Stable isotope evidence of dual (Arabian Sea and Bay of Bengal) vapour sources in monsoonal precipitation over north India

High resolution time series data of hydrogen (δD) and oxygen (δ¹⁸O) isotope values of precipitation have been generated for the first time at Kolkata, eastern India where the summer monsoon clouds from Bay of Bengal (BOB) commence their journey over India. Use of a Rayleigh cum two component mixing model and comparison of Kolkata data with the International Atomic Energy Agency (IAEA)–Global Network of Isotopes in Precipitation (GNIP) data base of New Delhi suggest that the precipitation at New Delhi cannot be explained by simple continental effect of a BOB vapour source alone, traveling and raining successively along Kolkata–New Delhi route. It is necessary to invoke an admixture of  20% vapour originating from the Arabian sea with the vapour coming from BOB and finally causing summer monsoon rains at New Delhi. The findings have major implications to the regional water vapour budget over India.     

Isotope geochemistry of Pantelleria volcanic fluids, Sicily Channel rift: a mantle volatile end-member for volcanism in southern Europe

Chemical and isotopic ratio (He, C, H and O) analysis of hydrothermal manifestations on Pantelleria island, the southernmost active volcano in Italy, provides us with the first data upon mantle degassing through the Sicily Channel rift zone, south of the African–European collision plate boundary. We find that Pantelleria fluids contain a CO₂–He-rich gas component of mantle magmatic derivation which, at shallow depth, variably interacts with a main thermal (100°C) aquifer of mixed marine–meteoric water. The measured ³He/⁴He ratios and δ¹³C of both the free gases (4.5–7.3 R_a and −5.8 to −4.2‰, respectively) and dissolved helium and carbon in waters (1.0–6.3 R_a and −7.1 to −0.9‰), together with their covariation with the He/CO₂ ratio, constrain a ³He/⁴He ratio of 7.3±0.1 R_a and a δ¹³C of ca. −4‰ for the magmatic end-member. These latter are best preserved in fluids emanating inside the active caldera of Pantelleria, in agreement with a higher heat flow across this structure and other indications of an underlying crustal magma reservoir. Outside the caldera, the magmatic component is more affected by air dilution and, at a few sites, by mixing with either organic carbon and/or radiogenic ⁴He leached from the U–Th-rich trachytic host rocks of the aquifer. Pantelleria magmatic end-member is richer in ³He and has a lower (closer to MORB) δ¹³C than all fluids yet analyzed in volcanic regions of Italy and southern Europe, including Mt. Etna in Sicily (6.9±0.2 R_a, δ¹³C=−3±1‰). This observation is consistent with a south to north increasing imprint of subducted crustal material in the products of Italian volcanoes, whose He and C (but also O and Sr) isotopic ratios gradually evolve towards crustal values northward of the African–Eurasian plate collision boundary. Our results for Pantelleria extend this regional isotopic pattern further south and suggest the presence of a slightly most pristine or ‘less contaminated’, ³He-richer mantle source beneath the Sicily Channel rift zone. The lower than MORB ³He/⁴He ratio but higher than MORB CO₂/³He ratio of Pantelleria volatile end-member are compatible with petro-geochemical evidence that this mantle source includes an upwelling HIMU–EM1-type asthenospheric plume component whose origin, according to recent seismic data, may be in the lower mantle.     

Oxygen isotope measurements of mammoth and reindeer skeletal remains: an archive of Late Pleistocene environmental conditions in Eurasian Arctic

58 samples of fossil mammoth and reindeer teeth and bones of various ages and coming from different locations were studied for the oxygen isotopic composition of their phosphate. Samples from Siberia have interstadial (Marine Isotope Stage 3), stadial (MIS 2), late-glacial and post-glacial ages. Russian and Ukrainian samples refer to the late-glacial and transitional (between the interstadial and glacial stages) time. The δ¹⁸O of palaeoenvironmental waters were calculated from the δ¹⁸O_p obtained from fossil samples by means of the isotope equations calibrated on modern specimens of elephants and deer respectively. The δ¹⁸O_w obtained are generally lighter than those measured nowadays in the same areas and not far from those measured on ice cores of Holocene age, the isotopic differences being not greater than a few δ units. The calculated values are also in fairly good agreement with some isotopic values obtained from Siberian permafrost samples. According to the results obtained it seems that the elephant and deer equations can be reasonably used respectively in the case of fossil mammoth and deer skeletons to evaluate environmental palaeowaters.     

Carbon isotopes in submarine basalts

High-sensitivity stepped extraction reveals two isotopically distinct forms of carbon in submarine basalt glasses: an isotopically light carbon component released by combustion from 200 to 600°C and an isotopically heavy CO₂ liberated from vesicles (magmatic carbon) from 600 to 1200°C. The δ¹³C_PDB of the low release temperature carbon varies from −24 to −30‰ and is believed to be surficial organic contamination. A survey of various types of oceanic glasses demonstrates that the δ¹³C of magmatic CO₂ varies from −4.2 to −7.5‰ in mid-ocean ridge basalt (MORB), from −2.8 to −6.7‰ in glasses from Hawaii and Explorer Seamount and from −7.7 to −16.3‰ in glasses from the Scotia Sea and Mariana Trough. Magmatic CO₂ in back-arc basin basalts (BABB) is on average 5‰ lighter than equivalent CO₂ in MORB and can be explained by the mixing in the source regions for BABB magmas of juvenile (MORB-like) CO₂ with an organic carbon component from subducted pelagic sediments. It is inferred that significant amounts of pelagic carbonate carbon (δ¹³C 0‰) must be recycled into the mantle.     

Mid-latitude Southern Indian Ocean response to Northern Hemisphere Heinrich events

The lack of temporal resolution and accurate chronology of Southern Ocean marine cores has hampered comparison of glacial millennial-scale oscillations between the Southern Ocean, Antarctic ice and other records from both hemispheres. In this study, glacial climate variability is investigated over the last 50 ka using a multi-proxy approach. A precise chrono-stratigraphy was developed on the high-sedimentation rate core MD94-103 (Indian Southern Ocean, 45°35′S 86°31′E, 3560 m water depth) by geomagnetic synchronization between the later core and NAPIS75, and ¹⁴C dates. High-resolution time-series of δ¹⁸O in planktonic foraminifera Globigerina bulloides and Neogloboquadrina pachyderma, and sea surface temperatures (SSTs) estimated from the alkenone U^K′₃₇ index and foraminifera assemblages have been generated. Temporal evolution of the two temperature proxy records is notably different during the last glacial period. While foraminifera data indicate a consistent cooling towards the last glacial maximum, anomalous warm glacial alkenone temperatures suggest a strong advection of warm “detrital” alkenones by surface waters of the Agulhas current. Superimposed to this general trend, during Heinrich events, foraminiferal SSTs point to warmer surface waters, while concurrent alkenone SSTs exhibit apparent coolings probably caused by enhanced local alkenone production. By analogy to modern observations, possible influence of ENSO-like conditions on the subantarctic Southern Ocean SSTs is discussed.     

Helium isotope geochemistry of some volcanic rocks from Saint Helena

³He/⁴He ratios have been measured for olivine and clinopyroxene phenocrysts in 7–15 m.y. old basaltic lavas from the island of St. Helena. Magmatic helium was effectively resolved from post-eruptive radiogenic helium by employing various extraction techniques, includingin vacuo crushing, and stepwise heating or fusion of the powders following crushing. The inherited³He/⁴He ratio at St. Helena is 4.3–5.9 R_A. Helium isotope disequilibrium is present within the phenocrysts, with lower³He/⁴He upon heating and fusion of the powders following crushing, due to radiogenic ingrowth or to -particle implantation from the surrounding(U + Th)-rich lavas.

A single crushing analysis for clinopyroxene in a basalt from Tubuaii gave³He/⁴He= 7.1 R_A.³He/⁴He ratios at St. Helena and Tubuaii (HIMU hotspots characterized by radiogenic Pb isotope signatures) are similar to³He/⁴He ratios previously measured at Tristan da Cunha and Gough Island (EM hotspots characterized by low²⁰⁶Pb/²⁰⁴Pb). Overall, the HeSrPb isotope systematics at these islands are consistent with a mantle origin as contiguous, heterogeneous materials, such as recycled crust and/or lithosphere.³He/⁴He ratios at HIMU hotspots are similar to mantle xenoliths which display nearly the entire range of Pb isotope compositions found at ocean islands, and are only slightly less than values found in mid-ocean ridge basalts (7–9 R_A). This suggests that the recycled materials were injected into the mantle within the last 10⁹ yrs.