Nuclear and incommensurate magnetic structure of NaFeGe2O6 between 5?K and 298?K and new data on multiferroic NaFeSi2O6

The compound NaFeGe₂O₆ was grown synthetically as polycrystalline powder and as large single crystals suitable for X-ray and neutron-diffraction experiments to clarify the low temperature evolution of secondary structural parameters and to determine the low temperature magnetic spins structure. NaFeGe₂O₆ is isotypic to the clinopyroxene-type compound aegirine and adopts the typical HT-C2/c clinopyroxene structure down to 2.5?K. The Na-bearing M2 polyhedra were identified to show the largest volume expansion between 2.5?K and room temperature, while the GeO₄ tetrahedra behave as stiff units. Magnetic susceptibility measurements show a broad maximum around 33?K, which marks the onset of low-dimensional magnetic ordering. Below 12?K NaFeGe₂O₆ transforms to an incommensurately modulated magnetic spin state, with k?=?[0.323, 1.0, 0.080] and a helical order of spins within the M1-chains of FeO₆ octahedra. This is determined by neutron-diffraction experiments on a single crystal. Comparison of NaFeGe₂O₆ with NaFeSi₂O₆ is given and it is shown that the magnetic ordering in the latter compound, aegirine, also is complex and is best described by two different spin states, a commensurate one with C2??/c?? symmetry and an incommensurate one, best being described by a spin density wave, oriented within the (1 0 1) plane.     

Geology,mineral chemistry and tourmaline B isotopes of the Córrego Bom Sucesso area,southern Serra do Espinhaço,Minas Gerais,Brazil: Implications for Au–Pd–Pt exploration in quartzitic terrain

The Palaeo-Mesoproterozoic metasiliciclastic rocks of the southern Serra do Espinhaço, Minas Gerais, Brazil, are host to historically important alluvial deposits of diamonds and gold. Detrital gold grains often comprise Au–Pd–Pt intermetallic compounds, with low Ag contents, which contain inclusions of tourmaline and titaniferous hematite (up to ~ 6 wt.% TiO₂). The latter minerals connect the alluvial mineralisation to the rutile–hematite–quartz veins and tourmalinisation observed in the quartzitic country rocks of the alluvial gravel. The quartzite (Sopa-Brumadinho Formation of lacustrine to fan-deltaic origin) is affected by pervasive B metasomatism with F-bearing tourmaline replacing the recrystallised quartz fabric. The tourmaline belongs to the alkali group, with Mg/(Mg + Fe) and X/(X + Na) ratios in the ranges from 0.5 to 0.7 and 0.18 to 0.29, respectively, where X represents vacancies in the X site. Boron-isotopic values of tourmaline vary from ~ 1 to − 10.4‰ δ¹¹B. The B-isotope range, in conjunction with the Na–Mg-rich tourmaline composition, and the widespread occurrence of tourmalinite in the Sopa-Brumadinho Formation suggest a derivation from non-marine evaporitic brines. Brines are capable of transporting otherwise immobile Ti and explain, under oxidising conditions, the fractionation of Ag from Pd to precipitate palladiferous gold with extremely high Pd/Ag ratios. Zirconium-in-rutile and Ti-in-quartz temperatures for a variety of hematite-rich veins suggest episodic vein emplacement over a temperature range from around 500 °C to ~ 350 °C. Cross-cutting relationships and episodic vein emplacement indicate a late-Brasiliano age.     

Geology and geochronology of the Betara region in south-southeastern Brazil: Evidence for possible Statherian (1.80–1.75 Ga) and Calymmian (1.50–1.45 Ga) extension events

The results of geological mapping, chemical analysis and radiometric dating of metabasic rocks of Betara Formation, and mapping and dating of those present in the Betara basement nucleus together with mylonitic granodiorite and syenogranite are reported here. U–Pb analysis of bulk zircon fractions from the metabasic rocks of the basement nucleus yielded a Statherian age of 1790 ± 22 Ma, while the metabasic rocks from the upper part of the Betara Formation yielded a Calymmian age between 1500 and 1450 Ma. This age is a minimum for the deposition of the Betara Formation. The older metabasic rocks are associated with post-tectonic, possibly anorogenic syenogranite, while the younger ones are gabbro or very porphyritic ankaramite whose REE patterns are consistent with crystallization from an N-MORB parent magma. The observations and data point to the probable events associated with extensional processes of the end of Paleoproterozoic and early Mesoproterozoic. Similar registers of Statherian (1.80–1.75 Ga) and Calymmian (1.50–1.45 Ga) extensional events are recorded in other parts of the South American and African continents. The Neoproterozoic witnessed the formation and junction of the tectonic slices which formed the Apiaí domain during the assemblage of western Gondwana.     

Mass fluxes of xenobiotics below cities: challenges in urban hydrogeology

Urban areas are the focus of major ecological, social and economical activity. They are thus also prime locations of increasing conflict with regard to water use and water protection. As a direct and/or indirect consequence of urban land use and human activity, urban water systems are frequently polluted with organic contaminants including waste water-born xenobiotics such as pharmaceuticals, personal care products (collectively known as PPCPs) and endocrine-active substances. This study reviews new integrated methodologies including flux calculations as well as chemical investigations for determining the impact of human activities on urban water systems and on processes within the urban watershed. The use of indicator substances, representing different contaminant sources and pathways, integral pumping tests and mass balance approaches are suitable alternatives within these environments. The issues are explored using contaminant mass balance examples from Halle/Saale and Leipzig, Germany.     

An institutional analysis of the sustainability of fisheries: Insights from FishBanks simulation game

FishBanks, a well-known fisheries management simulation game, was used to test the effect of institutional settings on the biological and economic performance of fisheries. The game was played by 48 groups of between 20 and 25 undergraduate Environmental Science students in two different time lengths (10 years versus 15 years) and institutional settings (open access versus regulated access through a resource management regime). Sessions run under an institutional regime for resource management performed better than those under open access in terms of fish population, aggregate asset value and income distribution amongst competing companies. Fleet size, a proxy for human pressure on the resource, had a more intense effect than the existence or not of an institutional setting. Results also indicate that once a critical threshold is reached in stock deterioration, institutions may be insufficient to revert change, suggesting ultimate environmental limits to the effectiveness of institutions.     

Investigating the presence of organochlorine pesticides and polychlorinated biphenyls in wild and farmed gilthead sea bream (Sparus aurata) from the Western Mediterranean sea

The presence of organochlorine pesticides and polychlorinated biphenyls in wild and farmed gilthead sea bream (Sparus aurata) from the Western Mediterranean, Spain, is investigated. These pollutants were determined in white and red muscle and liver by gas chromatography coupled to tandem mass spectrometry. Contaminant profiles present in both wild and farmed fish tissues include DDTs, PCBs and HCB. The highest concentrations of contaminants were found in liver, and an increase in pollutant levels was observed in autumn, before spawning. This fact is explained in light of increased food intake when sea water temperatures increase. Gilthead sea bream from Western Mediterranean populations showed significantly higher concentrations of DDTs and PCBs than farmed fish from the same area. This fact is attributed to the low level of organochlorine contaminants present in fish feed supplied to the cultured fish. The diet is highlighted as an important factor in understanding differences observed in organochlorine pollutants levels of fish tissues.     

Inshore/offshore gradients of imposex and organotin contamination in Nassarius reticulatus (L.) along the Portuguese coast

Imposex and organotin (OT) tissue contamination of the netted whelk Nassarius reticulatus (L.) were assessed in the continental shelves around the main estuaries of the central coast of Portugal (Lisbon: Tagus estuary; Setúbal: Sado estuary) and the main coastal lagoon in the Southern of Portugal (Faro: Ria Formosa). Pollution levels were higher in areas of more intense boat traffic and shipyard activities and imposex showed a clear decreasing gradient from the estuaries to the offshore, in relation to a similar gradient of tissue contamination by tributyltin. Remarkably, imposex was extensively spread over the adjacent continental shelves of Tagus and Sado estuaries. The current work shows that TBT pollution is undoubtedly a matter of concern not only for the above estuaries where harbours are implanted but also for the adjacent continental shelves, regardless the massive dilution of contaminants that may occur in these deeper areas.     

On the cumulant expansion up scaling of ground water contaminant transport equation with nonequilibrium sorption

The laboratory-scale ground water transport equation with nonequilibrium sorption reaction subjected to unsteady, nondivergence-free, and nonstationary velocity fields is up-scaled to the field-scale by using the ensemble-averaged equations obtained from the cumulant expansion ensemble-averaging method. It is found that existing ensemble-averaged equations obtained with the help of the cumulant expansion method for the system of linear partial differential equations are not second-order exact. Although the cumulant expansion methodology is designed for noncommuting operators, it is found that there are still commudativity requirements that need to be satisfied by the functions and constants exist in the coefficient matrix of the system of ordinary/partial differential equations. A reversibility requirement, which covers the commudativity requirements, is also proposed when applying the cumulant expansion method to a system of partial differential equations/a partial differential equation. The significance of the new velocity correction obtained in this study due to the applied second-order exact cumulant expansion is investigated on a numerical example with a linear trend in the distribution coefficient. It is found that the effect of the new velocity correction can be significant enough to affect the maximum concentration values and the plume center of mass in the case of a trending distribution coefficient in a physically heterogeneous environment.     

Rare earth elements in sediments of the Vigo Ria,NW Iberian Peninsula

The abundance and distribution of rare earth elements (REE) and their signatures in the Vigo Ria were studied from 50 samples of surface sediments and related to the geological formation in its watershed. The total amount of REE in the Ria is heterogeneous. It ranges from 220 mg kg⁻¹ in the southern middle Ria margin in the vicinity of the Galiñeiro geological shore complex, which contains REE-enriched minerals, to 2 mg kg⁻¹ near the Ria mouth due to dilution with high levels of carbonated biogenic particles (31% of Ca). Rare earth elements of the Ria sediments are considerably enriched in light-REE relative to heavy-REE (a LREE/HREE ratio of 9.7±1.6) and also show a slightly negative Eu-anomaly. Low European shale normalised REE patterns were distinguished in the innermost sediments of Vigo Ria, but were not correlated with Al. This suggests a minor contribution of REE from upstream freshwater inputs to the sediments in the middle Vigo Ria zone. Normalised REE ratios in the middle Ria imply that fine particles enriched in REE may be exported from the Ria to shelf mud patches and REE can be useful as sediment tracers of Ria input on the shelf.