Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.     

On the effectiveness of the ocean's biological pump in global CO2 scenarios

An evaluation is made of the effectiveness of the ocean's biological pump in driving the deep-sea excess CO₂ from the atmosphere. It is based on sediment-trap data available in the literature and on estimates of present and future inputs of anthropogenic nitrogen and phosphorous. The fraction of annual CO₂ production from fossil fuel combustion going into this sink turns out to be insignificant in the total budget of man-made CO₂. A discussion is presented on the formation of macroflocs under oceanic conditions, a process that has been believed to be important for the effectiveness of the biological pump.     

Model identification for hydrological forecasting under uncertainty

Methods for the identification of models for hydrological forecasting have to consider the specific nature of these models and the uncertainties present in the modeling process. Current approaches fail to fully incorporate these two aspects. In this paper we review the nature of hydrological models and the consequences of this nature for the task of model identification. We then continue to discuss the history (“The need for more POWER‘’), the current state (“Learning from other fields”) and the future (“Towards a general framework”) of model identification. The discussion closes with a list of desirable features for an identification framework under uncertainty and open research questions in need of answers before such a framework can be implemented.     

Molecular formulae of marine and terrigenous dissolved organic matter detected by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

The chemical structure of refractory marine dissolved organic matter (DOM) is still largely unknown. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR-MS) was used to resolve the complex mixtures of DOM and provide valuable information on elemental compositions on a molecular scale. We characterized and compared DOM from two sharply contrasting aquatic environments, algal-derived DOM from the Weddell Sea (Antarctica) and terrigenous DOM from pore water of a tropical mangrove area in northern Brazil. Several thousand molecular formulas in the mass range of 300-600 Da were identified and reproduced in element ratio plots. On the basis of molecular elemental composition and double-bond equivalents (DBE) we calculated an average composition for marine DOM. O/C ratios in the marine samples were lower (0.36 ± 0.01) than in the mangrove pore-water sample (0.42). A small proportion of chemical formulas with higher molecular mass in the marine samples were characterized by very low O/C and H/C ratios probably reflecting amphiphilic properties. The average number of unsaturations in the marine samples was surprisingly high (DBE = 9.9; mangrove pore water: DBE = 9.4) most likely due to a significant contribution of carbonyl carbon. There was no significant difference in elemental composition between surface and deep-water DOM in the Weddell Sea. Although there were some molecules with unique marine elemental composition, there was a conspicuous degree of similarity between the terrigenous and algal-derived end members. Approximately one third of the molecular formulas were present in all marine as well as in the mangrove samples. We infer that different forms of microbial degradation ultimately lead to similar structural features that are intrinsically refractory, independent of the source of the organic matter and the environmental conditions where degradation took place.     

Late Miocene to Early Pliocene blueschist from Taiwan and its exhumation via forearc extraction

Blueschist facies rocks in the Yuli Belt of Taiwan's Central Range record ongoing subduction of the Eurasian plate. We present a prograde Lu–Hf garnet–whole‐rock age of 5.1 ± 1.7 Ma from a retrogressed blueschist in the Yuli Belt. This age is considerably younger than the previously assumed age of 14–8 Ma for high‐pressure metamorphism in the Yuli Belt and represents the youngest Lu–Hf garnet age ever recorded for blueschist facies metamorphism. The age sheds new light on the palaeogeographic origin and exhumation scenario of the Yuli Belt. We propose that the Yuli Belt originated from the ocean–continent boundary of the Chinese passive margin. It was subducted eastward during collision with the Luzon island arc and rapidly exhumed when the forearc lithosphere was removed from above the continental slab by discrete subduction (extraction). This process reduces the pressure above the continental slab and may prompt the ascent of subducted crust into the opening gap. Thus, it can control the exhumation of high‐pressure rocks.     

Unraveling complex hydrogeological processes in Andean basins in south‐central Chile: An integrated assessment to understand hydrological dissimilarity

Groundwater storage, drainage, and interbasin water exchange are common hydrological processes but often difficult to quantify due to a lack of local observations. We present a study of three volcanic mountainous watersheds located in south‐central Chile (~36.9 ° S) in the Chillán volcanic complex (Chillán, Renegado, and Diguillín river basins). These are neighboring basins that are similar with respect to the metrics normally available for characterization everywhere (e.g., precipitation, temperature, and land cover). In a hydrological sense, similar (proportional) behavior would be expected if these catchments would be characterized with this general information. However, these watersheds show dissimilar behavior when analyzed in detail. The surface water balance does not fit for any of these watersheds individually; however, the water balance of the whole system can be explained by likely interbasin water exchanges. The Renegado river basin has an average annual runoff per unit of area on the order of 60–65% less than those of the Diguillín and Chillán rivers, which is contradictory to the hydrological similarity among the basins. To understand the main processes that control streamflow generation, two analyses were performed: (a) basin metrics (land cover, geologic, topographic, and climatological maps) and hydro‐meteorological data analyses and (b) a water balance model approach. The analyses contribute to a plausible explanation for the hydrogeological processes in the system. The soils, topography, and geology of the Chillán–Renegado–Diguillín system favor the infiltration and groundwater movements from the Renegado river basin, mainly to the neighboring Diguillín basin. The interbasin water exchanges affect hydrological similarity and explain the differences observed in the hydrological processes of these three apparently similar volcanic basins. The results highlight the complexity of hydrological processes in volcanic mountainous systems and suggest that a simple watershed classification approach based on widely available data is insufficient. Simple local analyses such as specific flow analysis with a review of the geology and morphology can contribute to a better understanding of the hydrology of volcanic mountainous areas.     

Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

Investigating controls on the thermal sensitivity of Pennsylvania streams

Stream temperature, an important measure of ecosystem health, is expected to be altered by future changes in climate and land use, potentially leading to shifts in habitat distribution for aquatic organisms dependent on particular temperature regimes. To assess the sensitivity of stream temperature to change in a region where such a shift has the potential to occur, we examine the variability of and controls on the direct relationship between air and water temperature across the state of Pennsylvania. We characterized the relationship between air and stream temperature via linear and nonlinear regression for 57 sites across Pennsylvania at daily and weekly timescales. Model fit (r²) improved for 92% (daily) and 65% (weekly) of sites for nonlinear versus linear relationships. Fit for weekly versus daily regression analysis improved by 0·08 for linear and 0·06 for nonlinear regression relationships. To investigate the mechanisms controlling stream temperature sensitivity to environmental change, we define ‘thermal sensitivity’ as the sensitivity of stream temperature of a given site to change in air temperature, quantified as the slope of the regression line between air and stream temperature. Air temperature accounted for 60–95% of the daily variation in stream temperature for sites at or above a Strahler stream order (SO) of 3, with thermal sensitivities ranging from low (0·02) to high (0·93). The sensitivity of stream temperature to air temperature is primarily controlled by stream size (SO) and baseflow contribution. Together, SO and baseflow index explained 43% of the variance in thermal sensitivity across the state, and 59% within the Susquehanna River Basin. In small streams, baseflow contribution was the major determinant of thermal sensitivity, with increasing baseflow contributions resulting in decreasing sensitivity values. In large streams, thermal sensitivity increased with stream size, as a function of accumulated heat throughout the stream network. Copyright © 2011 John Wiley & Sons, Ltd.