Improving estuarine net flux estimates for dissolved cadmium export at the annual timescale: Application to the Gironde Estuary

Dissolved Cd (Cd_D) concentrations along the salinity gradient were measured in surface water of the Gironde Estuary during 15 cruises (2001–2007), covering a wide range of contrasting situations in terms of hydrology, turbidity and season. During all situations dissolved Cd concentrations displayed maximum values in the mid-salinity range, reflecting Cd addition by chloride-induced desorption and complexation. The daily net Cd_D fluxes from the Gironde Estuary to the coastal ocean were estimated using Boyle's method. Extrapolating Cd_D concentrations in the high salinity range to the freshwater end member using a theoretical dilution line produced 15 theoretical Cd concentrations (Cd_D⁰), each representative of one distinct situation. The obtained Cd_D⁰ concentrations were relatively similar (201 ± 28 ng L⁻¹) when freshwater discharge Q was >500 m³ s⁻¹ (508 ≤ Q ≤ 2600 m³ s⁻¹), but were highly variable (340 ± 80 ng L⁻¹; 247–490 ng L⁻¹) for low discharge situations (169 ≤ Q ≤ 368 m³ s⁻¹). The respective daily Cd_D net fluxes were 5–39 kg day⁻¹, mainly depending on freshwater discharge. As this observation invalidates the existing method of estimating annual Cd_D net fluxes, we proposed an empirical model, using representative Cd_D⁰ values and daily freshwater discharges for the 2001–2007 period. Subsequent integration produced reliable Cd_D net flux estimates for the Gironde Estuary at the annual timescale that ranged between 3.8–5.0 t a⁻¹ in 2005 and 6.0–7.2 t a⁻¹ in 2004, depending on freshwater discharge. Comparing Cd_D net fluxes with the incoming Cd_D fluxes suggested that the annual net Cd_D addition in the Gironde Estuary ranged from 3.5 to 6.7 t a⁻¹, without any clear temporal trend during the past seven years. The annual Cd_D net fluxes did not show a clearly decreasing trend in spite of an overall decrease by a factor 6 in Cd gross fluxes during the past decade. Furthermore, in six years out of seven (except 2003), the annual Cd_D net fluxes even exceeded river borne total (dissolved + particulate) gross Cd fluxes into the estuary. These observations were attributed to progressive Cd desorption from both suspended particles and bottom sediment during various sedimentation–resuspension cycles induced by tidal currents and/or continuous dredging (navigation channel) and diverse intra-estuarine sources (wet deposition, urban sources, and agriculture). Provided that gross fluxes remain stable over time, dissolved Cd exportation from the Gironde Estuary to the coastal ocean may remain at the present level for the coming decade and the estuarine sedimentary Cd stock is forecast to decrease slowly.     

Evaluating Renewable Groundwater Stress with GRACE Data in Greece

Groundwater is a resilient water source and its importance is even greater in periods of drought. Areas such as the Mediterranean where adverse climate change effects are expected are bell‐weather locations for groundwater depletion and are of considerable interest. The present study evaluates renewable groundwater stress (RGS) as the ratio of groundwater use to groundwater availability, quantifying use as the trend in gravity recovery and climate experiment‐derived (GRACE) subsurface anomalies (ΔGW_trend) and renewable groundwater availability as mean annual recharge. Estimates for mean annual recharge for the various regions in Greece have been derived using numerical models. Our results highlight two RGS regimes in Greece (variable stress and unstressed) of the four characteristic stress regimes, that is, overstressed, variable stress, human‐dominated stress, and unstressed, defined as a function of the sign of use and the sign of groundwater availability (positive or negative). Variable stress areas are found in Central Greece (Thessaly region), where intensive agriculture results in negative ΔGW_trend values combined with positive mean annual recharge rates. RGS values range from ?0.05 to 0, indicating a low impact area. Within this region, adverse effects of groundwater overexploitation are already evident based on the negative GRACE anomalies; however, recharge is still positive, mitigating the effects of over‐pumping. The rest of Greek aquifers fall within the unstressed category, with RGS values from 0.02 to 0.05, indicating that the rate of use is less than the natural recharge rate.     

The first post‐injection seismic monitor survey at the Ketzin pilot CO2 storage site: results from time‐lapse analysis

The injection of CO₂ at the Ketzin pilot CO₂ storage site started in June 2008 and ended in August 2013. During the 62 months of injection, a total amount of about 67 kt of CO₂ was injected into a saline aquifer. A third repeat three‐dimensional seismic survey, serving as the first post‐injection survey, was acquired in 2015, aiming to investigate the recent movement of the injected CO₂. Consistent with the previous two time‐lapse surveys, a predominantly west–northwest migration of the gaseous CO₂ plume in the up‐dip direction within the reservoir is inferred in this first post‐injection survey. No systematic anomalies are detected through the reservoir overburden. The extent of the CO₂ plume west of the injection site is almost identical to that found in the 2012 second repeat survey (after injection of 61 kt); however, there is a significant decrease in its size east of the injection site. Assessment of the CO₂ plume distribution suggests that the decrease in the size of the anomaly may be due to multiple factors, such as limited vertical resolution, CO₂ dissolution, and CO₂ migration into thin layers, in addition to the effects of ambient noise. Four‐dimensional seismic modelling based on dynamic flow simulations indicates that a dynamic balance between the newly injected CO₂ after the second repeat survey and the CO₂ migrating into thin layers and being dissolved was reached by the time of the first post‐injection survey. In view of the significant uncertainties in CO₂ mass estimation, both patchy and non‐patchy saturation models for the Ketzin site were taken into consideration.     

Biodiversity Conservation in the REDD

Background

Forests occur across diverse biomes, each of which shows a specific composition of plant communities associated with the particular climate regimes. Predicted future climate change will have impacts on the vulnerability and productivity of forests; in some regions higher temperatures will extend the growing season and thus improve forest productivity, while changed annual precipitation patterns may show disadvantageous effects in areas, where water availability is restricted. While adaptation of forests to predicted future climate scenarios has been intensively studied, less attention was paid to mitigation strategies such as the introduction of tree species well adapted to changing environmental conditions.

Results

We simulated the development of managed forest ecosystems in Germany for the time period between 2000 and 2100 under different forest management regimes and climate change scenarios. The management regimes reflect different rotation periods, harvesting intensities and species selection for reforestations. The climate change scenarios were taken from the IPCC's Special Report on Emission Scenarios (SRES). We used the scenarios A1B (rapid and successful economic development) and B1 (high level of environmental and social consciousness combined with a globally coherent approach to a more sustainable development). Our results indicate that the effects of different climate change scenarios on the future productivity and species composition of German forests are minor compared to the effects of forest management.

Conclusions

The inherent natural adaptive capacity of forest ecosystems to changing environmental conditions is limited by the long life time of trees. Planting of adapted species and forest management will reduce the impact of predicted future climate change on forests.     

Relating 27-Day Averages of Solar,Interplanetary Medium Parameters,and Geomagnetic Activity Proxies in Solar Cycle 24

Solar Physics - During solar minimum, the Sun is relatively inactive with few sunspots observed on the solar surface. Consequently, we observe a smaller number of highly energetic events such as...     

Calorimetric study of the stability of spinelloids in the system NiAl2O4-Ni2SiO4

Enthalpies of solution in molten 2 PbO · B₂O₃ at 974 K were measured for four spinelloids, phases I (0.75 NiAl₂O₄ · 0.25 Ni₂SiO₄), II (0.60 NiAl₂O₄ · 0.40 Ni₂SiO₄), III and IV (0.50 NiAl₂O₄ · 0.50 Ni₂SiO₄) in the system NiAl₂O₄ · Ni₂SiO₄. The enthalpies (in cal per 4-oxygen mol) of formation from NiAl₂O₄ and Ni₂SiO₄ spinels are: phase I, 945±366; phase II, 1072±360; phase III, 2253±390; phase IV, 3565±544. Using these enthalpy data in combination with phase relations at high pressure at 1373 K, positive entropies of formation of the spinelloids from NiAl₂O₄ and Ni₂SiO₄ spinels were estimated (in cal mol^?1 K^?1): phase I, 1.2; phase II, 1.5; phase III, 2.0–2.3; phase IV, 3.0–3.1. The thermochemical data obtained above suggest that the spinelloids are “entropy-stabilized” phases with partially disordered cation distributions. The configurational entropies of the spinelloids were calculated based on the observed cation distribution in each spinelloid phase. The positive entropies of formation of the spinelloids from the spinel endmembers are due primarily to the configurational entropies although small positive vibrational entropy changes may also exist.     

Thermochemical study of glasses in the system NaAlSi3O8-KAlSi3O8-Si4O8 and the join Na1.6Al1.6Si2.4O8-K1.6Al1.6Si2.4O8

Enthalpies of solution in 2PbO · B₂O₃ at 981 K have been measured for glasses in the system albite-orthoclase-silica and along the join Na_1.6Al_1.6Si_2.4O₈-K_1.6Al_1.6Si_2.4O₈. The join KAlSi₃O₈-Si₄O₈ shows zero heat of mixing similar to that found previously for NaAlSi₃O₈-Si₄O₈ glasses. Albite-orthoclase glasses show negative heats of mixing symmetric about Ab₅₀Or₅₀ (W_n = ? 2.4 ± 0.8 kcal). Negative heats of (Na, K) mixing are also found at $\text{Si}\text{(Si + Al)}\text{= 0.6.}$ Ternary excess enthalpies of mixing in the glassy system Ab-Or-4Q are positive but rarely exceed 1 kcal mol^?1.Using earlier studies of the thermodynamic properties of the crystals, the present calorimetric data and the “two-lattice” entropy model, the albite-orthoclase phase diagram is calculated in good agreement with experimental data. Attempts to calculate albite-silica and orthoclase-silica phase diagrams reveal complexities probably related to significant (but unknown) mutual solid solubility between cristobalite and alkali feldspar and to the very small heat and entropy of fusion of SiO₂.     

Thermochemical study of glasses in the system CaMgSi2O6-CaAl2SiO6

High temperature solution calorimetry of glasses in the system CaMgSi₂O₆ (Di)-CaAl₂SiO₆ (CaTs) show them to have negative enthalpies of mixing with a regular enthalpy parameter, W_H, of -11.4 ± 0.7 kcal. Negative heats of mixing between alumina-rich and alumina-poor glasses seem to be a general phenomenon in aluminosilicates and are not confined only to glassy systems containing anorthite as a component. The thermodynamic behavior of glasses in the system SiO₂-Ca_0.5;AlO₂-CaMgO₂ appears to vary in a smooth fashion, with small positive heats of mixing near SiO₂ and substantial negative heats of mixing for other compositions. The exothermic behavior with increasing $\text{A1}\text{(Al + Si)}$ may be related to local charge balance of M²⁺ and Al³⁺. The negative heats of mixing in MgCaSi₂O₆-CaAl₂SiO₆, MgCaSi₂O₆-CaAl₂Si₂O₈ and NaAlSi₃O₈-CaAl₂Si₂O₈ glasses are in contrast to the positive heats of mixing found in MgCaSi₂O₆-CaAl₂SiO₆ (pyroxene) and NaAlSi₃O₈-CaAl₂Si₂O₈ (high plagioclase) crystalline solid solutions.     

On stilpnomelane in some Romanian Carpathian crystalline formations

Summary The stilpnomelane minerals in the epimetamorphic series of the Romanian Carpathians are divided into four genetic groups. Some ferrostilpnomelanes from metamorphic iron-, manganese- and sulfide-ores have been studied optically, chemically, by differential thermal analysis, thermogravimetric analysis, X-ray diffraction, and IR absorption spectroscopy. Several conclusions on the chemical constitution and the widespread occurence of ferrostilpnomelane in the metamorphic ores of the Carpathians are given.

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Über Stilpnomelan in einigen kristallinen Formationen in den rumänischen Karpaten

Zusammenfassung Die Stilpnomelanvorkommen aus dem epimetamorphen Kristallin der rumänischen Karpaten werden in vier genetische Gruppen eingeteilt. Einige aus metamorphosierten Eisen-, Mangan- und Sulfiderzen stammende Ferrostilpnomelane wurden optisch, chemisch, mit Differentialthermoanalyse, Thermogravimetrie, Röntgenbeugung und Ultrarot-Absorptionsspektroskopie untersucht. Als Schlußfolgerungen ergeben sich einige allgemeine Hinweise über die Zusammensetzung des Ferrostilpnomelans in den Kristallinerzen der Karpaten.

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Mit 5 Figures     

The quartz-coesite-stishovite transformations: new calorimetric measurements and calculation of phase diagrams

High temperature solution calorimetry of synthetic quartz, coesite and stishovite provides enthalpies of transition. ΔH₉₇₅⁰ for quartz-coesite and ΔH₂₉₈⁰ for coesite-stishovite transition are 320 ± 70 and 11700 ± 410 cal mol^?1, respectively. The present transformation enthalpy data represent a small but significant revision of those of Holm et al. Using the published phase equilibrium data, thermal expansivity, compressibility and heat capacity data, ΔS₉₇₅⁰ for the quartz-coesite and ΔS₂₉₈⁰ for the coesite-stishovite transition are ?1.2 ± 0.1 and ?1.0 ± 0.4 cal K^?1 mol^?1, respectively. These thermochemical data are used to calculate phase boundaries of the transitions. The calculated quartz-coesite transition boundary agrees well with the one determined experimentally by Bohlen and Boettcher. The calculated coesite-stishovite boundary is generally consistent with data by Yagi and Akimoto and by Suito.