Crystal and molecular structure and spectroscopic behavior of isotypic synthetic analogs of the oxalate minerals stepanovite and zhemchuzhnikovite

The crystal structure of synthetic stepanovite, Na[Mg(H₂O)₆][Fe(C₂O₄)₃]·3H₂O, and zhemchuzhnikovite, Na[Mg(H₂O)₆][Al_0.55Fe_0.45(C₂O₄)₃]·3H₂O, has been determined by single-crystal X-ray diffraction methods. The compounds are isotypic to each other and to the previously reported Na[Mg(H₂O)₆][M(C₂O₄)₃]·3H₂O (M: Cr, Al). They crystallize in the trigonal P3c1 space group with Z = 6 molecules per unit cell and (hexagonal axes) a = 17.0483(4), c = 12.4218(4) Å for the iron compound, and a = 16.8852(5), c = 12.5368(5) Å for the Al/Fe solid solution. Comparison of our crystallographic results with previous X-ray diffraction and chemical data of type stepanovite and zhemchuzhnikovite minerals provides compelling evidence that these natural materials possess the same crystal and molecular structure as their synthetic counterparts. It is shown that the originally reported unit cell for stepanovite represents a pronounced sub-cell and that the correct unit cell and space group are based on weak superstructure reflections. The infrared and Raman spectra of both synthetic analogs were also recorded and are briefly discussed.     

Simulation of Geological Contacts from Interpreted Geological Model Using Multiple-Point Statistics

Applications of multiple-point statistics (mps) algorithms to large non-repetitive geological objects such as those found in mining deposits are difficult because most mps algorithms rely on pattern repetition for simulation. In many cases, an interpreted geological model built from a computer-aided design system is readily available but suffers as a training image due to the lack of patterns repetitiveness. Porphyry copper deposits and iron ore formations are good examples of such mining deposits with non-repetitive patterns. This paper presents an algorithm called contactsim that focuses on reproducing the patterns of the contacts between geological types. The algorithm learns the shapes of the lithotype contacts as interpreted by the geologist, and simulates their patterns at a later stage. Defining a zone of uncertainty around the lithological contact is a critical step in contactsim, because it defines both the zones where the simulation is performed and where the algorithm should focus to learn the transitional patterns between lithotypes. A larger zone of uncertainty results in greater variation between realizations. The definition of the uncertainty zone must take into consideration the geological understanding of the deposit, and the reliability of the contact zones. The contactsim algorithm is demonstrated on an iron ore formation.     

Development of regional future climate change scenarios in South America using the Eta CPTEC/HadCM3 climate change projections: climatology and regional analyses for the Amazon, S?o Francisco and the Paraná River basins

The objective of this study is to assess the climate projections over South America using the Eta-CPTEC regional model driven by four members of an ensemble of the Met Office Hadley Centre Global Coupled climate model HadCM3. The global model ensemble was run over the twenty-first century according to the SRES A1B emissions scenario, but with each member having a different climate sensitivity. The four members selected to drive the Eta-CPTEC model span the sensitivity range in the global model ensemble. The Eta-CPTEC model nested in these lateral boundary conditions was configured with a 40-km grid size and was run over 1961–1990 to represent baseline climate, and 2011–2100 to simulate possible future changes. Results presented here focus on austral summer and winter climate of 2011–2040, 2041–2070 and 2071–2100 periods, for South America and for three major river basins in Brazil. Projections of changes in upper and low-level circulation and the mean sea level pressure (SLP) fields simulate a pattern of weakening of the tropical circulation and strengthening of the subtropical circulation, marked by intensification at the surface of the Chaco Low and the subtropical highs. Strong warming (4–6°C) of continental South America increases the temperature gradient between continental South America and the South Atlantic. This leads to stronger SLP gradients between continent and oceans, and to changes in moisture transport and rainfall. Large rainfall reductions are simulated in Amazonia and Northeast Brazil (reaching up to 40%), and rainfall increases around the northern coast of Peru and Ecuador and in southeastern South America, reaching up to 30% in northern Argentina. All changes are more intense after 2040. The Precipitation–Evaporation (P–E) difference in the A1B downscaled scenario suggest water deficits and river runoff reductions in the eastern Amazon and S?o Francisco Basin, making these regions susceptible to drier conditions and droughts in the future.     

Dry spells in the River Plata Basin: an approximation of the diagnosis of droughts using daily data

This study addresses the dry spells observed in the La Plata Basin using daily data from 94 observation stations during sampling periods from 1900 to 2005. Dry days were defined as having less than 0.3?mm of accumulated precipitation. This definition allowed for the assessment of the dryness in the La Plata Basin and a comparison with other regions. The main purpose of this study was to analyse dry spells, especially extreme cases (meteorological droughts), and assess them on a daily basis. Trends and low frequency of droughts were analysed using a general framework to detect and compare properties of dry states based on daily and annual time scales. The trends were estimated using two different methods. Overall, the trends showed a decrease, especially in the eastern basin region during the period of 1972?C1996. The results showed sporadic decreases in dry events and events of extreme dryness (droughts). Spectral structure permits an inference of low-frequency maxima and confirmed an inter-annual 2- to 3-year period of variability in drought occurrence for most of the basin. Furthermore, probabilistic distribution functions of dry spells at basin stations were analysed to confirm that they followed a geometric?Cbinomial distribution. Additional tests were used to determine whether there was a second threshold, using the Weibull and gamma adjustment models. In order to study spatial homogeneity, the field of dry spell maxima in the basin was generated using a vector array based on the occurrence date and length of the maximum spell. Due to the dependence of spell length on the annual cycle, the longest spells were observed from April to the beginning of winter in the Argentine northwest region and in the northern and western regions of the basin. The intensity of droughts decreased in the Pampas and Mesopotamia regions. The drought of 1988 was considered to be the longest dry spell in the basin. The water deficits from this drought resulted in Argentinean economic losses of more than four billion US dollars during 1988.     

Using Empirical Mode Decomposition to Filter Out Non-turbulent Contributions to Air–Sea Fluxes

A methodology based on Empirical mode decomposition (EMD) was used to filter out non-turbulent motions from measurements of atmospheric turbulence over the sea, aimed at reducing their contribution to eddy-covariance (EC) estimates of turbulent fluxes. The proposed methodology has two main objectives: (1) to provide more robust estimates of the fluxes of momentum, heat and CO\(_2\); and (2) to reduce the number of flux intervals rejected due to non-stationarity criteria when using traditional EC data processing techniques. The method was applied to measurements from a 28-day cruise (HALOCAST 2010) in the Eastern Pacific region. Empirical mode decomposition was applied to 4-h long time series data and used to determine the cospectral gap time scale, \(T_\mathrm{{gap}}\). Intrinsic modes of oscillation with characteristic periods longer than the gap scale due to non-turbulent motions were assumed and filtered out. Turbulent fluxes were then calculated for sub-intervals of length \(T_\mathrm{{gap}}\) from the filtered 4-h time series. In the HALOCAST data, the gap scale was successfully identified in 89% of the 4-h periods and had a mean of 37 s. The EMD approach resulted in the rejection of 11% of the flux intervals, which was much less than the 68% rejected when using standard filtering methods based on data non-stationarity. For momentum and sensible heat fluxes, the averaged difference in flux magnitude between the traditional and EMD approaches was small (3 and 1%, respectively). For the CO\(_2\) flux, the magnitude of EMD flux estimates was on average 16% less than fluxes estimated from linear detrended 10-min time series. These results provide evidence that the EMD method can be used to reduce the effects of non-turbulent correlations from flux estimates.     

Spatial and temporal changes in reef fish assemblages on disturbed coral reefs,north Pacific coast of Costa Rica

Benthic structure of coral reefs determines the availability of refuges and food sources. Therefore, structural changes caused by natural and anthropogenic disturbances can have negative impacts on reef‐associated communities. During the 1990s, coral reefs from Bahía Culebra were considered among the most diverse ecosystems along the Pacific coast of Costa Rica; however, recently they have undergone severe deterioration as consequence of chronic stressors such as El Niño‐Southern Oscillation and harmful algal blooms. Reef fish populations in this area have also been intensely exploited. This study compared reef fish assemblages during two periods (1995–1996 and 2014–2016), to determine whether they have experienced changes as a result of natural and anthropogenic disturbances. For both periods, benthic composition and reef fish abundance were recorded using underwater visual censuses. Live coral cover (LCC) decreased from 43.09 ± 18.65% in 1995–1996 to 1.25 ± 2.42% in 2014–2016 (U = 36, p < 0.05). Macroalgal cover (%) in 2014–2016 was sixfold higher than mean values reported for the Eastern Tropical Pacific region. Mean (±SD) fish species richness in 1995–1996 (36.67 ± 14.20) was higher than in 2014–2016 (23.00 ± 9.14; U = 20, p < 0.05). Over 40% of reef fish orders observed in 1995–1996 were not detected in the 2014–2016 surveys, including large‐bodied predators. Reduction in abundance of fish predators such as sharks, grunts, and snappers is likely attributed to changes in habitat structure. Herbivorous such as parrotfishes and pufferfishes increased their abundance at sites with low LCC, probably in response to predators decline and increased algal cover. These findings revealed significant degradation and drastic loss of structural complexity in coral reefs from Bahía Culebra, which now are dominated by macroalgae. The large reduction in structural complexity of coral reefs has resulted in the loss of diversity and key ecological roles (e.g., predation and herbivory), thus potentially reducing the resilience of the entire ecosystem.     

On the stability of the moments of the maximum entropy wind wave spectrum

The stability of some current wind wave parameters as a function of high-frequency cut-off and degrees of freedom of the spectrum has been numerically investigated when computed in terms of the moments of the wave energy spectrum.From the Pierson-Moskovitz wave spectrum type, a sea surface profile is simulated and its wave energy spectrum is estimated by the Maximum Entropy Method (MEM). As the degrees of freedom of the MEM spectral estimation are varied, the results show a much better stability of the wave parameters as compared to the classical periodogram and correlogram spectral approaches. The stability of wave parameters as a function of high-frequency cut-off result the same as obtained by the classical techniques.     

A large epeiric methanogenic Bambuí sea in the core of Gondwana supercontinent?

Carbon isotope compositions of both sedimentary carbonate and organic matter can be used as key proxies of the global carbon cycle and of its evolution through time,as long as they are acquired from waters where the dissolved inorganic carbon(DIC)is in isotope equilibrium with the atmospheric CO2.However,in shallow water platforms and epeiric settings,the influence of local to regional parameters on carbon cycling may lead to DIG isotope variations unrelated to the global carbon cycle.This may be especially true for the terminal Neoproterozoic,when Gondwana assembly isolated waters masses from the global ocean,and extreme positive and negative carbon isotope excursions are recorded,potentially decoupled from global signals.To improve our understanding on the type of information recorded by these excursions,we investigate the pairedδ^13Ccarb andδ^13Corg evolution for an increasingly restricted late Ediacaran-Cambrian foreland system in the West Gondwana interior:the basal Bambui Group.This succession represents a 1~(st)-order sedimentary sequence and records two majorδ^13Ccarb excursions in its two lowermost lower-rank sequences.The basal cap carbonate interval at the base of the first sequence,deposited when the basin was connected to the ocean,hosts antithetical negative and positive excursions forδ^13Ccarb andδ^13Corg,respectively,resulting inΔ^13C values lower than 25‰.From the top of the basal sequence upwards,an extremely positiveδ^13Ccarb excursion is coupled toδ^13Corg,reaching values of+14‰and-14‰,respectively.This positive excursion represents a remarkable basin-wide carbon isotope feature of the Bambui Group that occurs with only minor changes inΔ^13C values,suggesting change in the DIC isotope composition.We argue that this regional isotopic excursion is related to a disconnection between the intrabasinal and the global carbon cycles.This extreme carbon isotope excursion may have been a product of a disequilibria between the basin DIC and atmospheric CO2 induced by an active methanogenesis,favored by the basin restriction.The drawdown of sulfate reservoir by microbial sulfate reduction in a poorly ventilated and dominantly anoxic basin would have triggered methanogenesis and ultimately methane escape to the atmosphere,resulting in a^13C-enriched DIC influenced by methanogenic CO2.Isolated basins in the interior of the Gondwana supercontinent may have represented a significant source of methane inputs to the atmosphere,potentially affecting both the global carbon cycle and the climate.     

Monthly streamflow forecasting using neuro-wavelet techniques and input analysis

ABSTRACT

Combinations of low-frequency components (also known as approximations) resulting from the wavelet decomposition are tested as inputs to an artificial neural network (ANN) in a hybrid approach, and compared to classical ANN models for flow forecasting for 1, 3, 6 and 12 months ahead. In addition, the inputs are rewritten in terms of the flow, revealing what type of information was being provided to the network, in order to understand the effect of the approximations on the forecasting performance. The results show that the hybrid approach improved the accuracy of all tested models, especially for 1, 3 and 6 months ahead. The input analyses show that high-frequency components are more important for shorter forecast horizons, while for longer horizons, they may worsen the model accuracy.