Patterns of Ca/Sr and Sr/Sr variation before and after a whole watershed CaSiO3 addition at the Hubbard Brook Experimental Forest, USA

Forty-one metric tons of the mineral wollastonite (CaSiO₃) was applied to an 11.8 hectare watershed at the Hubbard Brook Experimental Forest (HBEF; White Mountains, New Hampshire, USA) with the goal of restoring the Ca estimated to have been depleted from the soil exchange complex by acid deposition. This experiment provided an opportunity to gain qualitative information on whole watershed hydrologic flow paths by studying the response of stream water chemistry to the addition of Ca. Because the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios of wollastonite strongly contrast that of other Ca sources in the watershed, the wollastonite-derived Ca can be identified and its amount estimated in various ecosystem components. Stream water chemistry at the HBEF varies seasonally due to shifts in the proportion of base flow and interflow. Prior to the wollastonite application, seasonal variations in ⁸⁷Sr/⁸⁶Sr ratios indicated that ⁸⁷Sr/⁸⁶Sr was higher during base flow than interflow, due largely to greater amounts of biotite weathering along deeper flow paths. After the application, Ca/Sr and ⁸⁷Sr/⁸⁶Sr changed markedly as the high Ca/Sr and low ⁸⁷Sr/⁸⁶Sr wollastonite dissolved and mixed with stream water. The Ca addition provided information on the response times of various flow paths and ion exchange processes to Ca addition in this small upland watershed. During the first year after the addition, wollastonite applied to the near stream zone dissolved and was partially immobilized by cation exchange sites in the hyporheic zone. In the second and third years after the addition we infer that much of this Ca and Sr was subsequently desorbed from the hyporheic zone and was exported from the watershed in stream flow. In the fourth through ninth years after the addition, Ca and Sr from wollastonite that had dissolved in upland soils was transported to the stream by interflow during wet periods when the ground water table was elevated. Between years three and nine the minimum annual Ca/Sr ratio (in late summer base flow) increased, providing evidence that Ca and Sr had increasingly infiltrated to the deepest flow paths. Strong seasonal variations in Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios of stream water resulted from the wollastonite addition to upland forest soils, and these ratios have become sensitive to changing flow paths during the annual cycle. Most notably, high flow events now produce large excursions in stream geochemistry toward the high Ca/Sr and low ⁸⁷Sr/⁸⁶Sr ratios of wollastonite. Nine years after the application we estimate that ∼360 kg of Ca from wollastonite has been exported from the watershed in stream flow. The rate of export of Ca from wollastonite dissolution has stabilized at about 11 kg of Ca per year, which accounts for ∼30% of the dissolved Ca in the stream water. Given that 19 metric tons of Ca were applied to the watershed, and assuming this current rate of loss, it should take over 1000 years for this added Ca to be transported from the watershed.     

A Note on Turbulence Stationarity and Wind Persistence Within the Stable Planetary Boundary Layer

This note presents initial results of an analysis of the stationarity of turbulence kinetic energy and the persistence of winds within the stable boundary layer (SBL). Measurements were made at 1.5 and 11 m above ground level from 0100 to 0600 local time on five nights during the JORNADA field experiment. The average stationarity ranged from about 160 to about 570 s. Wind persistence ranged from about ± 40° (3-min average) to about ± 36° (30-min average) on a weakly stable night, and from about ± 40° (3-min average) to about ± 27° (30-min average) on an strongly stable night. It is shown that, at 1.5 m, which we take to be within the surface layer, the average duration of stationarity of turbulent kinetic energy tends to correlate with the kurtosis of the heat flux; however, at 11 m, which we take to be outside of the surface layer, this correlation is poorly approximated.     

Change-point analysis for serially correlated summit temperatures in the Romanian Carpathians

Characterizing climatic changes in the high-altitude mountain regions helps scientists and policy makers understand the effects of such changes on water resources, economic development, and the health of ecosystems. This paper proposes a change-point analysis to determine the time and magnitude of summer temperature changes in the summit areas of Romanian Carpathians between 1961 and 2007. Due to their altitude, massiveness, and position, Romanian Carpathians are an important barrier for different types of air masses between Western and Southeastern Europe. The results show that the change in summer temperatures occurred shortly after 1980. The average magnitude of this change is consistent with changes occurring in other parts of Southern Europe in the same time period although the magnitude of changes at individual weather stations may differ substantially. We aided our analysis by a statistical method based on regression models with serially correlated ARMA errors.     

Environmental factors controlling the spatiotemporal distribution of microbial communities in a coastal, sandy aquifer system (Doñana, southwest Spain)

Currently, aquifers are considered to be ecosystems that interchange materials and energy with other systems located in their surroundings. The aquifer system of Doñana (southwest Spain) has been studied over recent decades from a hydrogeological point of view, although nothing is known about its biological or ecological aspects. In order to describe the general characteristics of its microbial communities, bacterial abundance, cell biomass, bacterial biomass and microbial activities of functional groups were investigated by sampling, over a 2-year period, 13 wells located in the vicinity of four very productive shallow lakes in the most superficial part of this coastal, sandy aquifer system. Multivariate analysis of variance (MANOVA) indicated differences in abundance and biomass variables among sampling locations, seasons and sampling locations × seasons. Principal component analysis showed that temperature and dissolved oxygen appeared to be the most important factors controlling the temporal variability of microbial communities. Hydrological connectivity between surface water and groundwater was important in the control of the spatiotemporal distribution of microbial communities. Due to this hydrological connection, the aquifer system and the wetlands constitute a unique entity, a unique ecosystem, called the “hydroecosystem”, where microbial communities could play a central ecological role.     

A two‐step process for the reflooding of the Mediterranean after the Messinian Salinity Crisis

The Messinian Salinity Crisis is well known to have resulted from a significant drop of the Mediterranean sea level. Considering both onshore and offshore observations, the subsequent reflooding is generally thought to have been very sudden. We present here offshore seismic evidence from the Gulf of Lions and re‐visited onshore data from Italy and Turkey that lead to a new concept of a two‐step reflooding of the Mediterranean Basin after the Messinian Salinity Crisis. The refilling was first moderate and relatively slow accompanied by transgressive ravinement, and later on very rapid, preserving the subaerial Messinian Erosional Surface. The amplitude of these two successive rises of sea level has been estimated at ≤500 m for the first rise and 600–900 m for the second rise. Evaporites from the central Mediterranean basins appear to have been deposited principally at the beginning of the first step of reflooding. After the second step, which preceeded the Zanclean Global Stratotype Section and Point, successive connections with the Paratethyan Dacic Basin, then the Adriatic foredeep, and finally the Euxinian Basin occurred, as a consequence of the continued global rise in sea level. A complex morphology with sills and sub‐basins led to diachronous events such as the so‐called ‘Lago Mare’.This study helps to distinguish events that were synchronous over the entire Mediterranean realm, such as the two‐step reflooding, from those that were more local and diachronous. In addition, the shoreline that marks the transition between these two steps of reflooding in the Provence Basin provides a remarkable palaeogeographical marker for subsidence studies.     

Radio source calibration for the Very Small Array and other cosmic microwave background instruments at around 30 GHz

Accurate calibration of data is essential for the current generation of cosmic microwave background (CMB) experiments. Using data from the Very Small Array (VSA), we describe procedures which will lead to an accuracy of 1 per cent or better for experiments such as the VSA and CBI. Particular attention is paid to the stability of the receiver systems, the quality of the site and frequent observations of reference sources. At 30 GHz the careful correction for atmospheric emission and absorption is shown to be essential for achieving 1 per cent precision.
The sources for which a 1 per cent relative flux density calibration was achieved included Cas A, Cyg A, Tau A and NGC 7027 and the planets Venus, Jupiter and Saturn. A flux density, or brightness temperature in the case of the planets, was derived at 33 GHz relative to Jupiter which was adopted as the fundamental calibrator. A spectral index at ∼30 GHz is given for each.
Cas A, Tau A, NGC 7027 and Venus were examined for variability. Cas A was found to be decreasing at 0.394 ± 0.019 per cent yr⁻¹ over the period 2001 March to 2004 August. In the same period Tau A was decreasing at 0.22 ± 0.07 per cent yr⁻¹. A survey of the published data showed that the planetary nebula NGC 7027 decreased at 0.16 ± 0.04 per cent yr⁻¹ over the period 1967–2003. Venus showed an insignificant (1.5 ± 1.3 per cent) variation with Venusian illumination. The integrated polarization of Tau A at 33 GHz was found to be 7.8 ± 0.6 per cent at position angle =148°± 3°.     

Using the Fisher–Shannon method to characterize continuous seismic signal during volcanic eruptions: application to 2011–2012 El Hierro (Canary Islands) eruption

We investigated the dynamics of the continuous seismic signal recorded before and during the 2011–2012 El Hierro eruption (Canary Islands) using the innovative approach of the Fisher–Shannon method, a suitable statistical tool for detecting dynamic changes in complex systems. Our findings identify dynamic changes in the seismic signal that can be correlated with different stress states of the magmatic setting and the plumbing system in the volcano at El Hierro. The results contribute to the understanding of the fracturing pattern in the crust during a new intrusion and eruption of an overpressurized batch of magma.     

Effects of sewage pollution and bacterial load on growth and oxidative balance in the freshwater mussel Diplodon chilensis

The effect of chronic exposure to Escherichia coli on morphometrical parameters, different antioxidant defenses, lipid peroxidation and protein oxidation has been studied in digestive gland of the freshwater mussel Diplodon chilensis in the laboratory during 6 weeks. In, a parallel field study, we evaluated morphometrical and oxidative stress parameters in digestive glands of mussels collected from a sewage polluted area (SMA) and from a pristine area (control). Both sites were characterized by analyzing bacteriological and physic-chemical parameters. In the laboratory D. chilensis was able to filter bacteria at high concentrations with a clearing rate of 0.510 ± 0.036 L/h per gram of dry soft tissue mass. The digestive gland mass to shell length ratio (DGM/SL), reduced glutathione (GSH), lipid peroxidation, as concentration of thiobartituric acid reactive substances (TBARS), and glutathione-S-transferase (GST) activity of mussels fed with bacteria were significantly higher than those of control mussels after the fourth week. Fecal bacteria in lake water samples were undetectable in the control, and higher than 24,000 MPN (most probable number)/100 mL in SMA. DGM/SL was higher in SMA. No differences between sites were observed in total lipid and protein content, neither in superoxide dismutase activity. GSH content was higher in SMA, with no difference in the oxidized form. GST activity and MDA were significantly higher in SMA but protein oxidation was not affected.     

Aluminum coprecipitates with Fe (hydr)oxides: Does isomorphous substitution of Al for Fe in goethite occur?

Iron (hydr)oxides are common in natural environments and typically contain large amounts of impurities, presumably the result of coprecipitation processes. Coprecipitation of Al with Fe (hydr)oxides occurs, for example, during alternating reduction-oxidation cycles that promote dissolution of Fe from Fe-containing phases and its re-precipitation as Fe-Al (hydr)oxides. We used chemical and spectroscopic analyses to study the formation and transformation of Al coprecipitates with Fe (hydr)oxides. In addition, periodic density functional theory (DFT) computations were performed to assess the structural and energetic effects of isolated or clustered Al atoms at 8 and 25 mol% Al substitution in the goethite structure. Coprecipitates were synthesized by raising the pH of dilute homogeneous solutions containing a range of Fe and Al concentrations (100% Fe to 100% Al) to 5. The formation of ferrihydrite in initial suspensions with ?20 mol% Al, and of ferrihydrite and gibbsite in initial suspensions with ?25 mol% Al was confirmed by infrared spectroscopic and synchrotron-based X-ray diffraction analyses. While base titrations showed a buffer region that corresponded to the hydrolysis of Fe in initial solutions with ?25 mol% Al, all of the Al present in these solutions was retained by the solid phases at pH 5, thus indicating Al coprecipitation with the primary Fe hydroxide precipitate. In contrast, two buffer regions were observed in solutions with ?30 mol% Al (at pH ∼2.25 for Fe³⁺ and at pH ∼4 for Al³⁺), suggesting the formation of Fe and Al (hydr)oxides as two separate phases. The Al content of initial coprecipitates influenced the extent of ferrihydrite transformation and of its transformation products as indicated by the presence of goethite, hematite and/or ferrihydrite in aged suspensions. DFT experiments showed that: (i) optimized unit cell parameters for Al-substituted goethites (8 and 25 mol% Al) in clustered arrangement (i.e., the formation of diaspore-like clusters) were in good agreement with available experimental data whereas optimized unit cell parameters for isolated Al atoms were not, and (ii) Al-substituted goethites with Al in diaspore-like clusters resulted in more energetically favored structures. Combined experimental and DFT results are consistent with the coprecipitation of Al with Fe (hydr)oxides and with the formation of diaspore-like clusters, whereas DFT results suggest isomorphous Al for Fe substitution within goethite is unlikely at ?8 mol% Al substitution.