Grain boundary diffusion of Si, Mg, and O in enstatite reaction rims: a SIMS study using isotopically doped reactants

Diffusion-controlled growth rates of polycrystalline enstatite reaction rims between forsterite and quartz were determined at 1,000 °C and 1 GPa in presence of traces of water. Iron-free, pure synthetic forsterite with normal oxygen and silicon isotopic compositions and quartz extremely enriched in ¹⁸O and ²⁹Si were used as reactants. The relative mobility of ¹⁸O and ²⁹Si in reactants and rims were determined by SIMS step scanning. The morphology of the rim shows that enstatite grows by a direct replacement of forsterite. Rim growth is modelled within a mass-conserving reference frame that implies advancement of reaction fronts from the initial forsterite-quartz interface in both directions. The isotopic compositions at the two reaction interfaces are controlled by the partial reactions Mg₂SiO₄=0.5 Mg₂Si₂O₆+MgO at the forsterite-enstatite, and MgO+SiO₂=0.5 Mg₂Si₂O₆ at the enstatite-quartz interface, implying that grain boundary diffusion of MgO is rate-controlling. Isotopic profiles show no silicon exchange across the propagating reaction interfaces. This propagation, controlled by MgO diffusion, is faster than the homogenisation of Si by self-diffusion behind the advancing fronts. From this, and using % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamiramaaDa % aaleaacaWGtbGaamyAaiaacYcacaWGfbGaamOBaaqaaiaadAfacaWG % VbGaamiBaaaaaaa!3DD2! D_Si,En^VolD_{Si,En}^{Vol} at dry conditions from the literature, results a % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGabmirayaafa % Waa0baaSqaaiaadofacaWGPbGaaiilaiaadweacaWGUbaabaaaaOGa % eqiTdqgaaa!3CCD! D￠_Si,En dD'_{Si,En}^{} \delta value of 3᎒^-24 m³ s^-1 at 1,000 °C. The isotopic profiles for oxygen are more complex. They are interpreted as an interplay between the propagation of the interfaces, the homogenisation of the isotope concentrations by grain boundary self-diffusion of O within the rim, and the isotope exchange across the enstatite-quartz interface, which was open to ¹⁸O influx from quartz. Because of overlapping diffusion processes, boundary conditions are unstable and D´_Ox,En' cannot be quantified. Using measured rim growth rates, the grain boundary diffusivity D´_MgO' of MgO in iron-free enstatite is 8᎒^-22 m³ s^-1 at 1,000 °C and 1 GPa. Experiments with San Carlos olivine (fo₉₂) as reactant reveal lower rates by a factor of about 4. Our results show that isotope tracers in rim growth experiments allow identification of the actual interface reactions, recognition of the rate-controlling component and further calculation of D´' values for specific components.     

Diffusion of divalent cations in garnet: multi-couple experiments

We demonstrate the possibility of studying several diffusion couples in a single run, i.e. under almost similar P–T–t– conditions, allowing direct comparison of the diffusion rates in different diffusion couples. Thus the duration of experimental study and the risk of failure of expensive experimental equipment can be decreased considerably. The diffusion experiments were carried out in piston-cylinder apparatus. Gem-quality garnets of almandine, spessartine and grossular compositions together with inclusion-rich eclogitic garnets were embedded in a powder of natural pyrope and annealed together under dry conditions at P = 1.9–3.2 GPa and T = 1,070–1,400°C. Diffusion profiles were measured by electron microprobe and fitted numerically on the basis of multicomponent diffusion theory. The datasets derived from different diffusion couples yields parameters of the Arrhenius equation for Ca, Mg and Fe in natural eclogitic garnets and Mg, Mn and Fe in gem-quality garnets. We have also studied the effect of grain-boundary diffusion in the sintered pyrope matrix on interdiffusion on the basis of 2D modeling. Under conditions analogous to those of our experimental runs, we show that observed irregularities in some measured diffusion profiles (not applied for the diffusion modeling) can be directly related to the superposition of local grain-boundary diffusion on dominant volume diffusion.     

Thickness of the mixed bottom layer in the Northern Atlantic

The thickness of the mixed bottom boundary layer (BBL) has been analyzed based on the CTD data at transoceanic sections in abyssal waters of the Northern Atlantic. The measurements were carried out at two transoceanic sections approximately along 48° N (ASV-99) and 5° N (AI-2000) in 1999 and 2000. These data, and the WOCE data obtained at four zonal sections (AR7E and AR12 along 57° N, AR01 along 24.5° S, and A06 along 7.5° N), were used for the calculation of the statistical characteristics of the BBL??s thickness H _B . The probability distribution function F(H _B ) was close to lognormal. The mean value ??H _B ?? at different latitudes was in the range from 30 to 60 m. The averaged BBL thickness = 46.1 m. The BBL??s thickness was about 1% of the ocean??s depth D; the ratio H _B /D was the minimum (0.8%) near the equator and increased up to 1.6% in the polar latitudes.     

Plastic particles in coastal pelagic ecosystems of the Northeast Pacific ocean

The purpose of this study was to examine the distribution, abundance and characteristics of plastic particles in plankton samples collected routinely in Northeast Pacific ecosystems, and to contribute to the development of ideas for future research into the occurrence and impact of small plastic debris in marine pelagic ecosystems. Plastic debris particles were assessed from zooplankton samples collected as part of the National Oceanic and Atmospheric Administration's (NOAA) ongoing ecosystem surveys during two research cruises in the Southeast Bering Sea in the spring and fall of 2006 and four research cruises off the U.S. west coast (primarily off southern California) in spring, summer and fall of 2006, and in January of 2007. Nets with 0.505 mm mesh were used to collect surface samples during all cruises, and sub-surface samples during the four cruises off the west coast. The 595 plankton samples processed indicate that plastic particles are widely distributed in surface waters. The proportion of surface samples from each cruise that contained particles of plastic ranged from 8.75 to 84.0%, whereas particles were recorded in sub-surface samples from only one cruise (in 28.2% of the January 2007 samples). Spatial and temporal variability was apparent in the abundance and distribution of the plastic particles and mean standardized quantities varied among cruises with ranges of 0.004-0.19 particles/m3, and 0.014-0.209 mg dry mass/m3. Off southern California, quantities for the winter cruise were significantly higher, and for the spring cruise significantly lower than for the summer and fall surveys (surface data). Differences between surface particle concentrations and mass for the Bering Sea and California coast surveys were significant for pair-wise comparisons of the spring but not the fall cruises. The particles were assigned to three plastic product types: product fragments, fishing net and line fibers, and industrial pellets; and five size categories: <1 mm, 1-2.5 mm, >2.5-5 mm, >5-10 mm, and >10 mm. Product fragments accounted for the majority of the particles, and most were less than 2.5 mm in size. The ubiquity of such particles in the survey areas and predominance of sizes <2.5 mm implies persistence in these pelagic ecosystems as a result of continuous breakdown from larger plastic debris fragments, and widespread distribution by ocean currents. Detailed investigations of the trophic ecology of individual zooplankton species, and their encounter rates with various size ranges of plastic particles in the marine pelagic environment, are required in order to understand the potential for ingestion of such debris particles by these organisms. Ongoing plankton sampling programs by marine research institutes in large marine ecosystems are good potential sources of data for continued assessment of the abundance, distribution and potential impact of small plastic debris in productive coastal pelagic zones.     

LMWOA (low molecular weight organic acid) exudation by salt marsh plants: Natural variation and response to Cu contamination

This work aimed to evaluate, in vitro, the capability of roots of two salt marsh plants to release low molecular weight organic acids (LMWOAs) and to ascertain whether Cu contamination would stimulate or not organic acids exudation. The sea rush Juncus maritimus and the sea-club rush Scirpus maritimus, both from the lower Douro river estuary (NW Portugal), were used. Plants were collected seasonally, four times a year in 2004, during low tide. After sampling, plant roots were washed for removal of adherent particles and immersed for 2 h in a solution that matched salinity (3) and pH (7.5) of the pore water from the same location to obtain plant exudates. In one of the seasons, similar experiments were carried out but spiking the solution with different amounts of Cu in order to embrace the range between 0 and 1600 nM. In the final solutions as well as in sediment pore water LMWOAs were determined by high performance liquid chromatography. Plants were able to release, in a short period of time, relatively high amounts of LMWOAs (oxalate, citrate, malate, malonate, and succinate). In the sediment pore water oxalate, succinate and acetate were also detected. Therefore, plant roots probably contributed to the presence of some of these organic compounds in pore water. Exudation differed between the plant species and also showed some seasonally variation, particularly for S. maritimus. The release of oxalate by J. maritimus increased with Cu increase in the media. However, exudation of the other LMWOAs did not seem to be stimulated by Cu contamination in the media. This fact is compatible with the existence of alternative internal mechanisms for Cu detoxification, as denoted by the fact that in media contaminated with Cu both plant species accumulated relatively high amounts (29–83%) of the initially dissolved Cu. This study expands our knowledge on the contribution of globally dominant salt marsh plants to the release of LMWOAs into the environment.     

Meteorological results of MONSOON-88 expedition (pre-monsoon period)

Mean atmospheric circulation, moisture budget and net heat exchange were studied during a pre-monsoon period (18th March to 3rd May, 1988), making use of the data collected on board Akademik Korolev in the central equatorial and southern Arabian Sea region. The net heat exchange (R _n ) is found to be about 20 W m^–2 for a small area (0–4° N; 55–60° E), 50% less than the dimatological value. The mean value of net radiation (140 W m^–2) is less than the climatological value, which was due to higher cloud amount. The higher SST enhanced both the latent and sensible heat fluxes.The mean atmospheric circulation obtained from the upper air data is quite convincing. The mean exchange coefficient (C _e ) estimated from the moisture budget is about 1.0 × 10^–3 for a wind speed of 4 m s^–1. This value is slightly lower than that obtained by the usual methods.National Institute of Oceanography, RC, 52-Kirlampudi layout, Visakhapatnam — 530 023.India Meteorological Department, Gauhati.     

Assessment of Indian summer monsoon simulation by Community Atmosphere Model (CAM3)

Seasonal prediction of Indian Summer Monsoon (ISM) has been attempted for the current year 2011 using Community Atmosphere Model (CAM) developed at the National Centre for Atmospheric Research (NCAR). First, 30?years of model climatology starting from 1981 to 2010 has been generated to capture the variability of ISM over the Indian region using 30 seasonal simulations. The simulated model climatology has been validated with different sets of observed climatology, and it was observed that the simulated climatological rainfall is affected by model bias. Subsequently, a bias correction procedure using the Tropical Rainfall Measuring Mission (TRMM) 3B43 rainfall has been proposed. The bias-corrected rainfall climatology shows both spatial and temporal variability of ISM satisfactorily. Further, four sets of 10-member ensemble simulations of ISM 2009 and 2010 have been performed in hindcast mode using observed sea surface temperature (SST) and persistence of April SST anomaly, and it has been found that the bias-corrected model rainfall captures the seasonal variability of ISM reasonably well with some discrepancies in these two contrasting monsoon years. With this positive background, the seasonal prediction of ISM 2011 has been carried out in forecast mode with the assumption of persistence of May SST anomaly from June through September 2011. The model assessment shows an 11% deficiency in All-India Rainfall (AIR) of ISM 2011. In particular, the monthly accumulated rains are predicted to be 101% (17.6?cm), 86% (24.3?cm), 83% (21.0?cm) and 95% (15.5?cm) of normal AIR for the months of June, July, August and September, respectively.     

Lysosomal membrane stability and metallothioneins in digestive gland of Mussels (Mytilus galloprovincialis Lam.) as biomarkers in a field study

The lysosomal membrane destabilization and the metallothionein content in the digestive gland cells of mussels (Mytilus galloprovincialis Lam.), collected along the east coast of the North Adriatic (Istrian and Kvarnerine coast, Croatia), were examined over a period of four years (1996–1999). The lysosomal membrane stability, as a biomarker of general stress, showed that the membrane labilization period in mussels from polluted, urban- and industrial-related areas was significantly decreased (p<0.05) when compared to mussels from control, clean sea water sites. In the harbour of Rijeka, the most contaminated site, the lysosomal membrane stability was reduced by more than 70% compared to the control. This method also proved to be a useful biomarker for detection of additional stress caused by short-term hypoxia that occurred once during this study inside the polluted and periodically quite eutrophic Pula Harbour. The concentration of metallothioneins in the mussel digestive gland, as a specific biomarker of exposure to heavy metals, did not reveal significant differences (p<0.05) between sites covered by this study.     

Secondary copper enrichment in tailings at the Laver mine, northern Sweden

 Field and laboratory studies of the sulphide-bearing tailings at Laver, northern Sweden, show that the present release of metals from the tailings is low, especially with regard to Cu. A large part of the Cu released by sulphide oxidation is enriched in a distinct zone just below the oxidation front. The enrichment zone occurs almost all over the tailings area except in areas with a shallow groundwater table. The Cu enrichment is caused by formation of covellite and adsorption onto mineral surfaces. The transport of Zn, Co, Cd, Ni and S seems to be controlled mainly by adsorption. No secondary zone or secondary minerals containing these metals have been found. Just below the groundwater table, metals are released into solution when the enrichment zone reaches the groundwater due to the low pH. An increased release of metals, especially Cu, can be expected in the future, since the enrichment zone is moving towards the groundwater table. Received: 4 December 1997 · Accepted: 17 December 1998