XAFS characterization of the structural site of Yb in synthetic pyrope and grossular garnets. II: XANES full multiple scattering calculations at the Yb LI- and LIII-edges

We present an X-ray absorption near-edge structure study performed at the Yb L_I- and L_III-edges on synthetic pyrope (Mg₃Al₂Si₃O₁₂) and grossular (Ca₃Al₂Si₃O₁₂) garnets containing about 1% wt of Yb. For the first time Yb L-edge XANES spectra are analyzed by full multiple scattering theory using clusters of different sizes and different final-state potentials. A comparison between experimental spectra and model calculations indicates that Yb³⁺ enters the dodecahedral X-site in both pyrope and grossular, in agreement with the results of an EXAFS study. Based on the present results, the charge balancing substitution mechanism required by the replacement of divalent Mg and Ca cations with trivalent Yb³⁺ is discussed in terms of vacancies in dodecahedral sites surrounding the central Yb³⁺ absorber. Received: 7 December 1998 / Revised, accepted: 7 May 1999     

Representivity of incompletely sampled fall deposits in estimating eruption source parameters: a test using the 12–13 January 2011 lava fountain deposit from Mt. Etna volcano,Italy

The Southeast Crater (SEC) of Mt. Etna, Italy, is renowned for its high activity, mainly long-lived eruptions consisting of sequences of individual paroxysmal episodes which have produced more than 150 eruptive events since 1998. Each episode typically forms eruption columns followed by tephra fallout over distances of up to about 100 km from the vent. One of the last sequences consisted of 25 lava fountaining events, which took place between January 2011 and April 2012 from a pit-vent on the eastern flank of the SEC and built a new scoria cone renamed New Southeast Crater. The first episode on 12–13 January 2011 produced tephra fallout which was unusually dispersed toward to the South extending out over the Mediterranean Sea. The southerly deposition of tephra permitted an extensive survey at distances between ~1 and ~100 km, providing an excellent characterization of the tephra deposit. Here, we document the stratigraphy of the 12–13 January fallout deposit, draw its dispersal, and reconstruct its isopleth map. These data are then used to estimate the main eruption source parameters. The total erupted mass (TEM) was calculated by using four different methodologies which give a mean value of 1.5?±?0.4?×?10⁸ kg. The mass eruption rate (MER) is 2.5?±?0.7?×?10⁴ kg/s using eruption duration of 100 min. The total grain-size (TGS) distribution, peaked at ?3 phi, ranges between ?5 and 5 phi and has a median value of ?1.4 phi. Further, for the eruption column height, we obtained respective values of 6.8–13.8 km by using the method of Carey and Sparks (1986) and 3.4?±?0.3 km by using the methods of Wilson and Walker (1987), Mastin et al. (2009), and Pistolesi et al. (2011) and considering the mean value of MER from the deposit. We also evaluated the uncertainty and reliability of TEM and TGS for scenarios where the proximal and distal samples are not obtainable. This is achieved by only using a sector spanning the downwind distances between 6 and 23 km. This scenario is typical for Etna when the tephra plume is dispersed eastward, i.e., in the prevailing wind direction. Our results show that, if the analyzed deposit has poorer sample coverage than presented in this study, the TEM (3.4?×?10⁷ kg) is 22 % than the TEM obtained from the whole deposit. The lack of the proximal (<6 km) deposit may cause more significant differences in the TGS estimations.     

Multidecadal variability of summer temperature over Romania and its relation with Atlantic Multidecadal Oscillation

We investigate the multidecadal variability of summer temperature over Romania as measured at 14 meteorological stations with long-term observational records. The dominant pattern of summer temperature variability has a monopolar structure and shows pronounced multidecadal variations. A correlation analysis reveals that these multidecadal variations are related with multidecadal variations in the frequency of four daily atmospheric circulation patterns from the North Atlantic region. It is found that on multidecadal time scales, negative summer mean temperature (TT) anomalies are associated with positive sea level pressure (SLP) anomalies centered over the northern part of the Atlantic Ocean and Scandinavia and negative SLP anomalies centered over the northern part of Africa. It is speculated that a possible cause of multidecadal fluctuations in the frequency of these four patterns are the sea surface temperature (SST) anomalies associated to the Atlantic Multidecadal Oscillation (AMO). These results have implications for predicting the evolution of summer temperature over Romania on multidecadal time scales.     

Consistency and fidelity of Indonesian-throughflow total volume transport estimated by 14 ocean data assimilation products

Monthly averaged total volume transport of the Indonesian throughflow (ITF) estimated by 14 global ocean data assimilation (ODA) products that are decade to multi-decade long are compared among themselves and with observations from the INSTANT Program (2004–2006). The main goals of the comparisons are to examine the consistency and evaluate the skill of different ODA products in simulating ITF transport. The ensemble averaged, time-mean value of ODA estimates is 13.6 Sv (1 Sv = 10⁶ m³/s) for the common 1993–2001 period and 13.9 Sv for the 2004–2006 INSTANT Program period. These values are close to the 15-Sv estimate derived from INSTANT observations. All but one ODA time-mean estimate fall within the range of uncertainty of the INSTANT estimate. In terms of temporal variability, the scatter among different ODA estimates averaged over time is 1.7 Sv, which is substantially smaller than the magnitude of the temporal variability simulated by the ODA systems. Therefore, the overall “signal-to-noise” ratio for the ensemble estimates is larger than one. The best consistency among the products occurs on seasonal-to-interannual time scales, with generally stronger (weaker) ITF during boreal summer (winter) and during La Nina (El Nino) events. The scatter among different products for seasonal-to-interannual time scales is approximately 1 Sv. Despite the good consistency, systematic difference is found between most ODA products and the INSTANT observations. All but the highest-resolution (18 km) ODA product show a dominant annual cycle while the INSTANT estimate and the 18-km product exhibit a strong semi-annual signal. The coarse resolution is an important factor that limits the level of agreement between ODA and INSTANT estimates. Decadal signals with periods of 10–15 years are seen. The most conspicuous and consistent decadal change is a relatively sharp increase in ITF transport during 1993–2000 associated with the strengthening tropical Pacific trade wind. Most products do not show a weakening ITF after the mid-1970s’ associated with the weakened Pacific trade wind. The scatter of ODA estimates is smaller after than before 1980, reflecting the impact of the enhanced observations after the 1980s. To assess the representativeness of using the average over a three-year period (e.g., the span of the INSTANT Program) to describe longer-term mean, we investigate the temporal variations of the three-year low-pass ODA estimates. The average variation is about 3.6 Sv, which is largely due to the increase of ITF transport from 1993 to 2000. However, the three-year average during the 2004–2006 INSTANT Program period is within 0.5 Sv of the long-term mean for the past few decades.     

Use of sedimentary pigments to infer past phosphorus concentration in lakes

We propose a palaeolimnological method for inferring past total phosphorus (TP) concentrations in lake water from spectrophotometrically-measured sedimentary pigments, particularly total carotenoids (TC). Our approach is based on a highly significant statistical correlation (P < 0.0001) between pigment concentrations (total carotenoids) in the surface sediment of 28 Italian lakes (subalpine, large, deep, shallow, volcanic) and TP concentrations measured in these lakes at overturn when the core was collected. A transfer function was developed from this “training” set, and used to estimate past TP concentrations from pigment concentrations in sediment cores. The results generally agreed with TP values as measured by long-term water quality monitoring programs. Contrasting results were obtained by a comparison with diatom-inferred TP. While the diatom model showed a tendency to overestimate TP values higher than 100 μg l⁻¹, the pigment model correctly estimated TP in lakes when TP was <100 μg l⁻¹, but not when lakes were rich in macrophytes. In fact, lakes with extensive populations of aquatic submersed macrophytes and epiphytes are outliers in terms of the TC versus TP relationship. The root mean square error of prediction of the pigment model is lower than those derived from certain diatom—based inference models. The predicted and residual values are not related to the estimated values and their average is not statistically different from zero. Errors were estimated via a ‘leave-one-out’ re-sampling technique. The proposed method permits rapid and relatively inexpensive determination of reference trophic conditions.     

Role of pigments on algal communities and photosynthesis

A one-year study of phytoplankton, primary production and related physical and chemical factors was made in a Swiss basin of Lake Lugano (Lago di Lugano). The chlorophylls and 12 carotenoids were analyzed with a TLC technique. The carotenoid monitoring was considered to be particularly interesting, because the role of these pigments in freshwater algae is still very poorly documented by field studies. The dependence of photosynthesis on several factors was statistically evaluated. Evidence was found of light-adaptation phenomena. The variations of photosynthetic activity and efficiency largely depended on the light regime in the few days before the field observations and on the cellular content of chlorophylls and single carotenoids, whose concentrations in their turn were closely linked with light, temperature, average cell size, and with the actual species assemblage.     

Technical paper: FluMo—a mobile fluid–chemical monitoring unit for geothermal plants

A versatile fluid–chemical monitoring unit has been developed in the framework of the geothermal research platform Groß Schönebeck, Germany. It enables selective online and in situ measurements of various physico-chemical parameters at different surface locations of a geothermal fluid loop. Sensors are provided for pressure, temperature, volumetric flow rate, density, pH-value, redox potential, oxygen content, and electrical conductivity. In addition, the apparatus features two fluid samplers to manually collect fluid under in situ conditions and ultimately analyze the solution composition. All devices are mounted on a rack allowing easy transfer of the apparatus to other geothermal plants. The maximum operating pressure and temperature of the unit are 15 bar and 150 °C, respectively. The scientific and technical purpose of the system is to monitor a compositional variability of the produced fluid and chemical processes potentially occurring within the plant. These may result from reactions between the fluid and the surrounding materials, e.g., corrosion. Also, mineral precipitation as a consequence of temperature and/or pressure decrease or oxygen contamination may occur. This information is of paramount importance as so induced reactions might lead to failure of plant components or may damage the geothermal reservoir upon fluid reinjection and thus decrease injectivity.