Thermal expansion and decomposition of jarosite: a high-temperature neutron diffraction study

The structure of deuterated jarosite, KFe₃(SO₄)₂(OD)₆, was investigated using time-of-flight neutron diffraction up to its dehydroxylation temperature. Rietveld analysis reveals that with increasing temperature, its c dimension expands at a rate ~10 times greater than that for a. This anisotropy of thermal expansion is due to rapid increase in the thickness of the (001) sheet of [Fe(O,OH)₆] octahedra and [SO₄] tetrahedra with increasing temperature. Fitting of the measured cell volumes yields a coefficient of thermal expansion, α = α₀ + α₁ T, where α₀ = 1.01 × 10⁻⁴ K⁻¹ and α₁ = −1.15 × 10⁻⁷ K⁻². On heating, the hydrogen bonds, O1···D–O3, through which the (001) octahedral–tetrahedral sheets are held together, become weakened, as reflected by an increase in the D···O1 distance and a concomitant decrease in the O3–D distance with increasing temperature. On further heating to 575 K, jarosite starts to decompose into nanocrystalline yavapaiite and hematite (as well as water vapor), a direct result of the breaking of the hydrogen bonds that hold the jarosite structure together.     

EPMA and PIXE dating of monazite in granulites from Stary Gierałtów, NE Bohemian Massif, Poland

Chemical Th–U–total Pb (CHIME) dating of monazite by electron probe microanalyzer (EPMA) and proton microprobe (PIXE) was carried out on felsic granulites from Stary Gierałtów, Poland, which represent part of the Orlica-Śnieżnik Dome in the NE Bohemian Massif. Analyzed monazite is characterized by mosaic zoning rather than simple core-to-rim growth, and strontium contents of up to 750ppm. An isochron age of 347 ± 13Ma represents timing of amphibolite-facies metamorphism, in agreement with previously published estimates.     

An estuarine benthic index of biotic integrity (B-IBI) for Chesapeake Bay

A multimetric benthic index of biotic integrity (B-IBI) was developed using data from five Chesapeake Bay sampling programs conducted between 1972 and 1991. Attributes of the index were selected by comparing the response of 17 candidate measures of benthic condition (metrics) between a set of minimally affected reference sites and at all other sites for which data were available. This procedure was conducted independently for each of seven habitats defined by salinity and substrate. Fifteen of the 17 candidate metrics differed significantly between reference sites and other sites for at least one habitat. No metric differed significantly in all seven habitats; however, four metrics, species diversity, abundance, biomass, and percent of abundance as pollution-indicative taxa, differed in six habitats. The index was calculated by scoring each selected metric as 5, 3, or 1 depending on whether its value at a site approximated, deviated slightly from, or deviated greatly from conditions at the best reference sites. Validation based on independent data collected between 1992 and 1994 indicated that the index correctly distinguished stressed sites from reference sites 93% of the time, with the highest validation rates occurring in high salinity habitats.     

Shifts in Zooplankton Community Structure: Implications for Food Web Processes in the Upper San Francisco Estuary

Zooplankton are an important trophic link and a key food source for many larval fish species in estuarine ecosystems. The present study documents temporal and spatial zooplankton dynamics in Suisun Bay and the Sacramento–San Joaquin Delta—the landward portion of the San Francisco Estuary (California, USA)—over a 37-year period (1972–2008). The zooplankton community experienced major changes in species composition, largely associated with direct and indirect effects of introductions of non-native bivalve and zooplankton species. A major clam invasion and many subsequent changes in zooplankton abundance and composition coincided with an extended drought and accompanying low-flow/high-salinity conditions during 1987–1994. In the downstream mesohaline region, the historically abundant calanoid copepods and rotifers have declined significantly, but their biomass has been compensated to some extent by the introduced cyclopoid Limnothoina tetraspina. The more upstream estuary has also experienced long-term declining biomass trends, particularly of cladocerans and rotifers, although calanoid copepods have increased since the early 1990s due to the introduced Pseudodiaptomus spp. In addition, mysid biomass has dropped significantly throughout the estuary. Shifts in zooplankton species composition have also been accompanied by an observed decrease in mean zooplankton size and an inferred decrease in zooplankton food quality. These changes in the biomass, size, and possibly chemical composition of the zooplankton community imply major alterations in pelagic food web processes, including a drop in prey quantity and quality for foraging fish and an increase in the importance of the microbial food web for higher trophic levels.     

Hypoxia and benthic community recovery in Korean coastal waters

Low dissolved oxygen (hypoxia and/or anoxia) has become a major cause of change to the benthic component of ecosystems around the world. We present the response of a benthic community to hypoxia in organically enriched environments in Korean coastal waters. Disturbances due to low dissolved oxygen (DO), and organic enrichment altered community dynamics, result in defaunation during summer hypoxia with delayed recolonization occurring in winter. As DO decreased, the number of taxa, their abundance and biomass of macrofauna dropped significantly at inner bay stations in Chinhae Bay and Youngsan River estuarine bay affected by hypoxia. With the return of normoxic conditions in Chinhae Bay, recolonization was initiated by opportunistic species, with a 1-4months lag. The polychaetes, Sigambra tentaculata, Mesochaetopterus sp., and Lumbrineris longifolia, were most persistent under hypoxia. The first recolonizers were the polychaetes Paraprionospio pinnata, S. tantaculata, Glycinde gurjanovae and Nectoneanthes multignatha and the bivalve Theora fragilis. The second group of colonizers included the polychaetes Capitella capitata, Mesochaetopterus sp. and L. longifolia, and the bivalve Raetellops pulchella. Hypoxic and near anoxic conditions resulted in mass mortality in Chinhae Bay and Youngsan River estuarine bay, but communities did partially recover after return to normoxic conditions despite delayed recolonization.     

Stability of Titanium Dioxide Nanoparticle Agglomerates in Transitional Waters and Their Effects Towards Plankton from Lagoon of Venice (Italy)

The present study explores the effect of salinity and dissolved organic carbon (DOC) gradients on the stability and reactivity of titanium dioxide nanoparticle (TiO₂-NP) agglomerates in ambient water from the Lagoon of Venice and their possible effect on nauplii sampled at the same locations. In all ambient water samples, TiO₂-NPs formed rapidly micrometre-sized agglomerates. The increase in the salinity and concomitant decrease in DOC content induced the formation of larger agglomerates, with z-average hydrodynamic diameter increasing with TiO₂-NP concentration and exposure duration. Under the studied conditions, ζ-potential exhibited negative values. In line with agglomeration results, enhancement of the salinity and lower DOC resulted in less negative ζ-potential with close to 0 values in the dispersions of 100 mg L^?1 TiO₂-NPs in sea water. Two-hour exposure to micrometre-sized agglomerates of TiO₂-NPs resulted in an increase in the fluorescence of propidium iodide (PI) stained nauplii in comparison with unexposed controls, but had no effect at 24-h exposure. The increase in nauplii-associated PI fluorescence was more noticeable in dispersions containing 100 mg L^?1 than those containing 10 mg L^?1 TiO₂-NPs, suggesting membrane permeability alteration in a concentration-dependent manner. However, the PI staining results have to be interpreted with caution because of the possible dye binding to the nauplii surface without penetration of cellular membrane. The effect of TiO₂-NPs on nauplii was more pronounced at higher salinity and decreased with increasing DOC concentrations at 2 h, while no trends were found at 24-h exposure, as well as exposure to 100 mg L^?1 TiO₂-NPs.     

Factors Influencing Helophyte Distribution in Lakes (Eastern Poland)

Water Resources - The aim of the study was to show which morphometric traits of lakes influence the development of the rush zone of lakes and how buffer zone management influences analyzed features...     

The role of Fischer‐Tropsch catalysis in solar nebula chemistry

Abstract— Fischer‐Tropsch catalysis, the iron/nickel catalyzed conversion of CO and H₂ to hydrocarbons, would have been the only thermally‐driven pathway available in the solar nebula to convert CO into other forms of carbon. A major issue in meteoritics is to determine the origin of meteoritic organics: are they mainly formed from CO in the solar nebula via a process such as Fischer‐Tropsch, or are they derived from interstellar organics? In order to determine the role that Fischer‐Tropsch catalysis may have played in the organic chemical evolution of the solar nebula, we have developed a kinetic model for this process. Our model results agree well with experimental data from several existing laboratory studies. In contrast, empirical rate equations, which have been derived from experimental rate data for a limited temperature (T) and pressure (P) range, are inconsistent with experimental rate data for higher T and lower P. We have applied our model to pressure and temperature profiles for the solar nebula, during the epoch in which meteorite parent bodies condensed and agglomerated. We find that, under nebular conditions, the conversion rate of CO to CH₄ does not simply increase with temperature as the empirically‐derived equations suggest. Instead, our model results show that this process would have been most efficient in a fairly narrow region that coincides with the present position of the asteroid belt. Our results support the hypothesis that Fischer‐Tropsch catalysis may have played a role in solar nebula chemistry by converting CO into less volatile materials that can be much more readily processed in the nebula and in parent bodies.     

Monitoring CO2 saturation using time‐lapse amplitude versus offset analysis of 3D seismic data from the Ketzin CO2 storage pilot site,Germany

The injection of CO₂ at the Ketzin pilot site commenced in June 2008 and was terminated in August 2013 after 67 kT had been injected into a saline formation at a depth of 630–650 m. As part of the site monitoring program, four 3D surface seismic surveys have been acquired to date, one baseline and three repeats, of which two were conducted during the injection period, and one during the post‐injection phase. The surveys have provided the most comprehensive images of the spreading CO₂ plume within the reservoir layer. Both petrophysical experiments on core samples from the Ketzin reservoir and spectral decomposition of the 3D time‐lapse seismic data show that the reservoir pore pressure change due to CO₂ injection has a rather minor impact on the seismic amplitudes. Therefore, the observed amplitude anomaly is interpreted to be mainly due to CO₂ saturation. In this study, amplitude versus offset analysis has been applied to investigate the amplitude versus offset response from the top of the sandstone reservoir during the injection and post‐injection phases, and utilize it to obtain a more quantitative assessment of the CO₂ gaseous saturation changes. Based on the amplitude versus offset modelling, a prominent decrease in the intercept values imaged at the top of the reservoir around the injection well is indeed associated solely with the CO₂ saturation increase. Any change in the gradient values, which would, in case it was positive, be the only signature induced by the reservoir pressure variations, has not been observed. The amplitude versus offset intercept change is, therefore, entirely ascribed to CO₂ saturation and used for its quantitative assessment. The estimated CO₂ saturation values around the injection area in the range of 40%–60% are similar to those obtained earlier from pulsed neutron‐gamma logging. The highest values of 80% are found in the second seismic repeat in close vicinity to the injection and observation wells.     

Determination of volatile concentrations in fluorapatite of Martian shergottite NWA 2975 by combining synchrotron FTIR,Raman spectroscopy,EMPA, and TEM,and inferences on the volatile budget of the apatite host‐magma

We combined the focused ion beam sample preparation technique with polarized synchrotron‐based FTIR (Fourier transform infrared) spectroscopy, laser‐Raman spectroscopy, electron microprobe analysis (EMPA), and transmission electron microscope (TEM) analysis to identify and quantify structurally bound OH, F, Cl, and CO₃ groups in fluorapatite from the Northwest Africa 2975 (NWA 2975) shergottite. In this study, the first FTIR spectra of the OH‐stretching region from a Martian apatite are presented that show characteristic OH‐bands of a F‐rich, hydroxyl‐bearing apatite. Depending on the method of apatite‐formula calculation and whether charge balance is assumed or not, the FTIR‐based quantification of the incorporated OH, expressed as wt% H₂O, is in variably good agreement with the H₂O concentration calculated from electron microprobe data. EMP analyses yielded between 0.35 and 0.54 wt% H₂O, and IR data yielded an average H₂O content of 0.31 ± 0.03 wt%, consistent with the lower range determined from EMP analyses. The TEM observations implied that the volatiles budget of fluorapatite is magmatic. The water content and the relative volatile ratios calculated for the NWA 2975 magma are similar to those established for other enriched or intermediate shergottites. It is difficult to define the source of enrichment: either Martian wet mantle or crustal assimilation. Comparing the environment of parental magma generation for NWA 2975 with the terrestrial mantle in terms of water content, it displays a composition intermediate between enriched and depleted MORB.