Characterisation of Fulvic Acids and Glycyrrhizic Acid by Time‐of‐Flight Secondary Ion Mass Spectrometry

Fulvic acids of different origin, spray deposited on polished silicon after dissolution in high‐purity water without any additives, were analysed by time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) in combination with oblique 24...36 keV SF₅⁺ ion bombardment. The observed, highly reproducible mass spectra cover more than five orders of magnitude in dynamic range, without background subtraction. Apart from lines due to atomic ions and low‐mass ion fragments, the mass spectra exhibit broad maxima between m/z 200...350, mainly due to a beat‐like superposition of lines at every single mass number, up to at least m/z 400. In the negative ion spectra the beats have a spacing of m/z 14, corresponding to a CH₂‐unit. The high‐mass tails of the spectra extend well beyond m/z 5000, with similar slopes in the positive and the negative ion mass spectra. The negative spectra appear to be less affected by fragmentation products than the positive spectra. Fulvic acids (FAs) of different origin show distinctly different spectra, with mean masses ranging between m/z ≈ 450 and 580 (for a low‐mass cut‐off m/z 150). To further verify the ability of TOF‐SIMS to detect molecules and clusters with masses significantly above the maxima of the FA spectra, samples of glycyrrhizic acid (GA, as GA ammonium salt with molecular weight 840) were also analysed. Parent ions as well as multimers (GA)_n were observed as positive and negative ions, up to n = 4 (m/z 3320). The results are compared with spectra recently obtained by other mass spectrometric techniques.     

Modeling reactive transport in non-ideal aqueous–solid solution system

The numerical simulation of reactive mass transport processes in complex geochemical environments is an important tool for the performance assessment of future waste repositories. A new combination of the multi-component mass transport code GeoSys/RockFlow and the Gibbs Energy Minimization (GEM) equilibrium solver GEM-Selektor is used to calculate the accurate equilibrium of multiple non-ideal solid solutions which are important for the immobilization of radionuclides such as Ra. The coupled code is verified by a widely used benchmark of dissolution–precipitation in a calcite–dolomite system. A more complex application shown in this paper is the transport of Ra in the near-field of a nuclear waste repository. Depending on the initial inventories of Sr, Ba and sulfate, non-ideal sulfate and carbonate solid solutions can fix mobile Ra cations. Due to the complex geochemical interactions, the reactive transport simulations can describe the migration of Ra in a much more realistic way than using the traditional linear K_D approach only.     

Insights into the Structure and Surface Geology of Isla Socorro,Mexico, from Airborne Magnetic and Gamma-Ray Surveys

The island of Socorro is located in the eastern Pacific Ocean, 650 km off the coast of Mexico. It is a rare example of an oceanic volcanic island whose above sea level volume is made up mostly of peralkaline trachytes and rhyolites, with subordinate mafic rocks. Subaerial volcanism started several hundred thousand years ago and continues until recent times. We present an investigation of surface and subsurface geology of the island, based on the first detailed extensive geophysical survey on the island. Acquired airborne magnetic and gamma-ray data were compared to existing geological information and supplemented with field investigations and satellite imagery. Magnetic data show a wide minimum in the central part of the island, possibly connected to a high-temperature zone in the deeper central portion of the volcano, likely to be due to a still hot magma body. The data also depict two parallel edges possibly suggesting the existence of a nested caldera. Analysis on upward continued magnetic data by recent imaging techniques highlighted two deep sources located around 5 km b.s.l., interpreted as feeding structures that are now filled with crystalline rocks. Gamma-ray data have been interpreted through integration with the geological survey results. Several previously known volcanic deposits have been identified based on radioelement distribution, and others have been redefined based on field evidence. A new succession of volcanic members is proposed, to be verified through more detailed geological mapping, geochemical analyses of rock samples and radiometric dating.     

Gravity field contribution analysis of GOCE gravitational gradient components

A gravity field model is computed from the four accurate gravitational gradient components of GOCE (Gravity field and steady-state Ocean Circulation Explorer), combined with the analysis of the kinematic orbits, and some moderate constraint (or stabilization) in the polar areas where no observation from GOCE is available due to the orbit geometry. The normal matrix of each component is computed individually in order to study its contribution to the combined solution. The results show that the contribution of V_zz is the largest, with an average value of 32.74% of the total solution; the second and the third largest are V_zz and V_yy, with average values of 28.04% and 26.08%, respectively; the component V_xz contributes 11.81%. Validation with external data shows that each component has its characteristic value and that the information content of the component V_xz is not negligible and should be included for gravity field recovery. The orbit part as derived from high-low satellite-to-satellite tracking (SST-hl) to the GPS contributes mostly to the coefficients below degree and order (d/o) 20, and to non-zonal coefficients from d/o 20 to 80. The mean value of the contribution of the polar stabilization is the smallest with a value of 0.22%, nevertheless it is important. In addition to the contribution analysis in terms of the normal matrices, each individual component of the gradiometer has been combined with SST and polar stabilization, to give a set of single component gravity field models. These partially combined solutions are compared to the fully combined solution in terms of geoid differences. They show that the partially combined solution with V_zz is closest to the complete solution. Even closer is a combination with V_xx and V_yy. In addition to the GOCE-only solution, a GOCE-GRACE (Gravity Recovery And Climate Experiment) combined gravity field model is derived and the information content of GOCE and an available set of normal equations of GRACE are investigated. Results show that, as expected, GRACE dominates the solution below degree 90 and GOCE above degree 140.     

Evaluation of the first GOCE static gravity field models using terrestrial gravity,vertical deflections and EGM2008 quasigeoid heights

Recently, four global geopotential models (GGMs) were computed and released based on the first 2 months of data collected by the Gravity field and steady-state Ocean Circulation Explorer (GOCE) dedicated satellite gravity field mission. Given that GOCE is a technologically complex mission and different processing strategies were applied to real space-collected GOCE data for the first time, evaluation of the new models is an important aspect. As a first assessment strategy, we use terrestrial gravity data over Switzerland and Australia and astrogeodetic vertical deflections over Europe and Australia as ground-truth data sets for GOCE model evaluation. We apply a spectral enhancement method (SEM) to the truncated GOCE GGMs to make their spectral content more comparable with the terrestrial data. The SEM utilises the high-degree bands of EGM2008 and residual terrain model data as a data source to widely bridge the spectral gap between the satellite and terrestrial data. Analysis of root mean square (RMS) errors is carried out as a function of (i) the GOCE GGM expansion degree and (ii) the four different GOCE GGMs. The RMS curves are also compared against those from EGM2008 and GRACE-based GGMs. As a second assessment strategy, we compare global grids of GOCE GGM and EGM2008 quasigeoid heights. In connection with EGM2008 error estimates, this allows location of regions where GOCE is likely to deliver improved knowledge on the Earth’s gravity field. Our ground truth data sets, together with the EGM2008 quasigeoid comparisons, signal clear improvements in the spectral band ~160–165 to ~180–185 in terms of spherical harmonic degrees for the GOCE-based GGMs, fairly independently of the individual GOCE model used. The results from both assessments together provide strong evidence that the first 2 months of GOCE observations improve the knowledge of the Earth’s static gravity field at spatial scales between ~125 and ~110 km, particularly over parts of Asia, Africa, South America and Antarctica, in comparison with the pre-GOCE-era.     

Spatial Patterns in Water Quality Associated with Submersed Plant Beds

This study describes the influence of submersed plant beds on spatial distributions of key water quality variables. An on-board flow-through water sampling system was used to investigate patterns in turbidity, chlorophyll-a, temperature, dissolved oxygen, and pH across a robust stand of the submersed plant Stuckenia pectinata. Spatially interpolated maps show that water quality conditions were significantly altered within this plant bed, especially during months of peak biomass, and that reduction of suspended particles focused at the bed’s edge. Comparison with a suite of submersed plant beds indicated that patterns were related to canopy height, shoot density, and cross-shore bed width. Wide and dense stands with tall canopies showed reduced turbidity and increased light penetration, while smaller sparser beds often showed elevated within-bed turbidity. These results suggest that bed effects on water quality conditions vary seasonally with plant canopy architecture and bed size, providing tentative guidelines for restoring self-sustaining beds.     

Response of juvenile lemon sharks, Negaprion brevirostris, to a magnetic barrier simulating a beach net

Beach nets are preventative devices used to minimize interactions between potentially harmful sharks and unsuspecting swimmers. Quantitative studies demonstrated that beach nets drastically reduced local elasmobranch populations, as well as caused considerable bycatch mortality. For this experiment, a beach net-like device was constructed and the behaviors of six juvenile lemon sharks (Negaprion brevirostris) were analyzed. Induced by olfactory and gustatory cues, sharks were given the choice to swim through a magnetic or control opening in the net. In the first trial, all six sharks avoided the magnetic region and significantly preferred to swim through the control region of the fence. The magnetic stimulus no longer affected the swimming behavior of three sharks retested after resting 24 h. Results from the retested sharks were correlated with those from repeated tonic immobility trials, which demonstrated a linear decrease in sensitivity to repeated magnetic stimulation. This study serves as a baseline experiment demonstrating that permanent magnets may substantially decrease elasmobranch mortality within beach nets.     

Major and trace element geochemistry of Lake Bogoria and Lake Nakuru,Kenya, during extreme draught

The physico-chemical properties of water samples from the two athalassic endorheic lakes Bogoria and Nakuru in Kenya were analysed. Surface water samples were taken between July 2008 and October 2009 in weekly intervals from each lake. The following parameters were determined: pH, salinity, electric conductivity, dissolved organic carbon (DOC), the major cations (FAAS and ICP-OES) and the major anions (IC), as well as certain trace elements (ICP-OES). Samples of superficial sediments were taken in October 2009 and examined using Instrumental Neutron Activation Analysis (INAA) for their major and trace element content including rare earth elements (REE). Both lakes are highly alkaline with a dominance of Na > K > Si > Ca in cations and HCO₃ > CO₃ > Cl > F > SO₄ in anions. Both lakes also exhibited high concentrations of Mo, As and fluoride. Due to an extreme draught from March to October 2009, the water level of Lake Nakuru dropped significantly. This created drastic evapoconcentration, with the total salinity rising from about 20‰ up to 63‰. Most parameters (DOC, Na, K, Ca, F, Mo and As) increased with falling water levels. A clear change in the quality of DOC was observed, followed by an almost complete depletion of dissolved Fe from the water phase. In Lake Bogoria the evapoconcentration effects were less pronounced (total salinity changed from about 40‰ to 48‰). The distributions of REE in the superficial sediments of Lake Nakuru and Lake Bogoria are presented here for the first time. The results show a high abundance of the REE and a very distinct Eu depletion of Eu/Eu* = 0.33–0.45.     

Ecosystem Responses of the Subtropical Kaneohe Bay,Hawaii, to Climate Change: A Nitrogen Cycle Modeling Approach

The global coastal zone is characterized by high biological productivity and serves as an important channel through which materials are transferred from land to the open ocean, yet little is known how it will be affected by climate change. Here, we use Kaneohe Bay, Hawaii, a semi-enclosed subtropical embayment partially surrounded by a mountainous watershed and fed by river runoff as an example to explore the potential impact of climate change on the pelagic and benthic cycling of nitrogen. We employ a nine-compartment nitrogen cycle biogeochemical box model and perturb it with a set of four idealized climate scenarios. We find that hydrological changes play a dominant role in determining the ecosystem structure, while temperature changes are more important for the trophic state and stability of the ecosystem. The ecosystem stability against storm events does not significantly change under any scenario. The system remains autotrophic in the future; however, it becomes significantly less autotrophic under drier climate, while it turns slightly more autotrophic under wetter climate. These findings may have implications for other high island watershed and coastal ecosystems in the tropics and subtropics.