Influence of glass composition and alteration solution on leached silicate glass structure: A solid-state NMR investigation

A multinuclear solid-state NMR investigation of the structure of the amorphous alteration products (so called gels) that form during the aqueous alteration of silicate glasses is reported. The studied glass compositions are of increasing complexity, with addition of aluminum, calcium, and zirconium to a sodium borosilicate glass. Two series of gels were obtained, in acidic and in basic solutions, and were analyzed using ¹H, ²⁹Si, and ²⁷Al MAS NMR spectroscopy. Advanced NMR techniques have been employed such as ¹H-²⁹Si and ¹H-²⁷Al cross-polarization (CP) MAS NMR, ¹H double quantum (DQ) MAS NMR and ²⁷Al multiple quantum (MQ) MAS NMR. Under acidic conditions, ²⁹Si CP MAS NMR data show that the repolymerized silicate networks have similar configuration. Zirconium as a second nearest neighbor increases the ²⁹Si isotropic chemical shift. The gel porosity is influenced by the pristine glass composition, modifying the silicon-proton interactions. From ¹H DQ and ¹H-²⁹Si CP MAS NMR experiments, it was possible to discriminate between silanol groups (isolated or not) and physisorbed molecular water near Si (Q²), Si (Q³), and Si (Q⁴) sites, as well as to gain insight into the hydrogen-bonding interaction and the mobility of the proton species. These experiments were also carried out on heated samples (180 °C) to evidence hydrogen bonds between hydroxyl groups on molecular water. Alteration in basic media resulted in a gel structure that is more dependent on the initial glass composition. ²⁷Al MQMAS NMR data revealed an exchange of charge compensating cations of the [AlO₄]⁻ groups during glass alteration. ¹H-²⁷Al CP MAS NMR data provide information about the proximities of these two nuclei and two aluminum environments have been distinguished. The availability of these new structural data should provide a better understanding of the impact of glass composition on the gel structure depending on the nature of the alteration solution.     

Records of environmental and climatic changes during the late Holocene from Svalbard: palaeolimnology of Kongressvatnet

A multi-core, multidisciplinary palaeolimnological study of the partially varved sediment of a deep, meromictic, arctic lake, Kongressvatnet (Svalbard, Western Spitsbergen), provides a record of environmental and climatic changes during last ca. 1800 years. The chronology of sedimentation was established using several dating techniques (¹³⁷Cs, ²¹⁰Pb, varve counts, palaeomagnetic correlation). A multiproxy record of palaeolimnological variability was compiled based on sedimentation rates, magnetic properties, varve thickness, organic matter, geochemistry, pigments from algal and photosynthetic bacteria, mineralogy and biological assemblages (diatoms, Cladocera). The major features recognised in our master core K99-3 include a shift in sediment source and supply (magnetic measurements, geochemistry) probably caused by glaciological changes in the catchment around 38–32 cm core depth (AD 700–820). Additional environmental changes are inferred at 20–18, 8–4.5 and 3–2 cm (AD ca. 1160–1255; 1715–1880; 1940–1963, respectively). During the past ca. 120 years a prominent sedimentological change from brownish-grey, partly laminated silt-clay (varves) to black organic-rich deposits was observed. From AD 1350 to AD1880 the sediment is comprised of a continuous sequence of varves, whereas the earlier sediments are mostly homogeneous with only a few short intercalated laminated sections between AD 860 and 1350. Sedimentation and accumulation rates increased during the last 30 years (modern warming). Pigment concentrations are very low in the lower ca. 32 cm of the core (AD 820) probably because of the high turbidity high energy environment. The high sulphur content in the uppermost 32 cm of sediment has given rise to two horizontally stratified populations of sulphur anaerobic photosynthetic bacteria, as inferred from their specific carotenoids. These bacteria populations are much more abundant during the Little Ice Age (LIA) than during warmer periods (e.g., during the Medieval Warm Period and 20th century). Diatoms are lacking from the core base up to 18 cm (ca. AD 1255); at this level, species indicative of mesotrophic water are present, whereas from 17 cm to the top of the core, oligotrophic taxa such as Staurosira construens/S. pinnata complex dominate, indicating extended ice coverage and more oligotrophic waters during the LIA. The concentration of Cladocera subfossil remains (dominated by Chydorus) are relatively high in the deepest sections (54–32 cm), whereas the upper 32 cm are characterized by a very low concentration of remains, possibly because of the strongly anoxic conditions, and in this upper sediment section rotifer resting eggs become prevalent. We interpret these changes as responses to climate forcing through its impact on glacial melt water, lake ice cover duration and mainly redox conditions in deep water. The observed changes suggest that at least some of our recorded changes may parallel the Greenland Ice core, although our study added more details about the inferred climatic changes. Further aspects are discussed, such as catchment processes, glacial activity, duration of the Medieval Warm Period, the Little Ice Age, local human activity, and limnology.     

A multigrid solver for 3D electromagnetic diffusion

The performance of a multigrid solver for the time‐harmonic electromagnetic problem in geophysical settings is investigated. The frequencies are sufficiently small for waves travelling at the speed of light to be negligible, so that a diffusive problem remains. The discretization of the governing equations is obtained by the finite‐integration technique, which can be viewed as a finite‐volume generalization of Yee's staggered grid scheme. The resulting set of discrete equations is solved by a multigrid method. The convergence rate of the multigrid method decreased when the grid was stretched. The slower convergence rate of the multigrid method can be compensated by using bicgstab2 , a conjugate‐gradient‐type method for non‐symmetric problems. In that case, the multigrid solver acts as a preconditioner. However, whereas the multigrid method provides excellent convergence with constant grid spacings, it performs less than satisfactorily when substantial grid stretching is used.     

Diatom stratigraphy of the last 250 ka at Lake El’gygytgyn,northeast Siberia

Diatom species counts were conducted on 171 sediment samples from the 13-m-long core PG1351 from Lake El’gygytgyn, northeast Siberia. The planktonic Cyclotella ocellata-complex dominates the diatom assemblage through most of the core record, persisting through a variety of climate conditions. Periphytic diatoms, although less abundant, have greater diversity and greater down-core assemblage variation. During warm climate modes, longer summer ice-free conditions may have allowed more complex diatom communities to develop in shallow-water habitats, and enhanced circulation may have increased transport of these diatoms to deeper parts of the lake. Zones of low overall diatom abundance further support inferred intervals of low lake productivity during times of extended lake ice and snow cover. More data on the modern spatial and temporal distribution of diatom species in the Lake El’gygytgyn system will improve inferences from core records. This is the last in a series of eleven papers published in this␣special issue dedicated to initial studies of El'gygytgyn Crater Lake and its catchment in NE Russia. Julie Brigham-Grette, Martin Melles, Pavel Minyuk were guest editors of this special issue.     

Diatoms from the genus Achnanthidium in flowing waters of the Appalachian Mountains (North America): Ecology, distribution and taxonomic notes

Diatoms from the genus Achnanthidium are abundant in rivers, streams, and springs of the Appalachian Mountains. They inhabit clean and polluted waters, including those affected by acid mine drainage. The identification of Achnanthidium taxa is difficult due to their small cell size and insufficient information in the diatom floras. We studied the taxonomy and ecology of Achnanthidium in Appalachian rivers by analyzing a data set of benthic diatom samples and corresponding water chemistry data collected during several water-quality surveys from 181 sampling sites. Ten species were identified using scanning electron and light microscopy: A. alpestre (Lowe & Kociolek) Lowe & Kociolek, A. atomus (Hustedt) Monnier, Lange-Bertalot, & Ector, A. deflexum (Reimer) Kingston, A. duthii (Sreenivasa) Edlund, A. eutrophilum (Lange-Bertalot) Lange-Bertalot, A. cf. gracillimum (Meister) Lange-Bertalot, A. cf. latecephalum Kobayasi, A. minutissimum (Kützing) Czarnecki (sensu lato), A. reimeri (Camburn) comb. nov., and A. rivulare Potapova & Ponader. The distribution of common taxa in relation to water chemistry was studied by fitting non-parametric regression models (generalized additive models, GAM, and non-parametric multiplicative regression models, NPMR) to species relative abundances. Studied Achnanthidium species differed considerably in their responses to water chemistry. These results suggest that species-level identifications will lead to more accurate bioassessments.     

Enhanced pumping test using physicochemical tracers to determine surface-water/groundwater interactions in an alluvial island aquifer,river Rhône,France

Groundwater extracted from the Barthelasse Island aquifer, surrounded by the river Rhône (southeastern France), contributes to the drinking water supplies of 180,000 inhabitants. Owing to its location close to the river and the presence of two backwaters (oxbow lakes), the pumped groundwater is highly vulnerable to river pollution. A pumping test was conducted over 24 h to analyse and quantify the water exchange processes between the river, backwaters and groundwater. During the pumping test, isotopic (δ¹⁸O, δ²H and ²²²Rn), hydrochemical and hydrophysical monitoring of the groundwater was undertaken. Hydraulic heads were measured in pumping wells and at a piezometer located between the wells. Discrete water samples were collected at several observation points in the field, including the backwater and river. The results show mixing between three end-members, as defined by the deuterium excess and silica concentration, led by river Rhône water which had been affected by water–rock interactions over time and mixing with surface evaporated waters. The pumped water resulted from mixing between three end-members, all of which depended on the river Rhône but differed in terms of residence time in the system. Although the groundwater pumping wells are close to each other (<70 m) and have similar depths, the changes in the contributions from end-member waters at each well were different during the pumping test. Comparing isotopic tracers and geochemistry made it possible to quantify the different hydrological compartments that contribute to the groundwater pumped from the boreholes, which is critical in constructing a conceptual flow model.

     

Short-term changes in the aerosol characteristics at Kharagpur (22°19′N, 87°19′E) during winter

In-situ measurements of number density, size distribution, and mass loading of near-surface aerosols were carried out at Kharagpur, a site on the eastern part of Indo-Gangetic Plains during the winter month of December 2004. The data have been used to investigate wintertime characteristics of aerosols and their effects on the occurrence of haze. The aerosol number density is found to be of the order of 10⁹ m^?3 and mass loading is ~265±70 μg m^?3 (5–8 times that reported from south Indian sites). The diurnal patterns and day-to-day variations in aerosol number density and mass loading are closely associated with atmospheric boundary layer height. During haze events, the number density of submicron particles is found to be 2–5 times higher than that during non-hazy period. This could be attributed to the enhanced concentration of anthropogenic aerosols, low atmospheric boundary layer height/ventilation coefficient and airflow convergence.     

ENAA Studies of pollution in anoxic Black Sea sediments

The vertical distributions of five potential pollutants - Zn, As, Br, Sn, and Sb - were determined via epithermal neutron activation in the upper 50 cm of unconsolidated sediments from the Black Sea, which were collected 600 m below sea surface. This analysis demonstrated increasing concentrations towards the upper limits of sediments, which were greater than alert concentrations in the case of As and Br, and in accordance with Romanian Environment Regulations. The utilization of Chernobyl ¹³⁷Cs as a time marker allowed for dating of this region to the last 100 years.     

Evaluating ecological quality in the north-eastern Black Sea coastal zone

Anthropogenic pressures have resulted in measurable impacts on the coastal ecosystems of the northern (Sevastopol Bay, Ukraine) and eastern (Batumi aquatoria, Georgia) Black Sea. Indices suggest that major impacts are relatively localized and are comparable to similar situations in the northern Atlantic. In contrast, biodiversity was appreciably lower than from comparable north Atlantic waters. The number of macrobenthic species was typically round 50, less than half the number that might be expected from similar exercises in US or European waters. Site-specific indices likewise indicated a somewhat lower diversity within communities, yielding metrics which would indicate a measure of stress in N. Atlantic situations. Microbial status was generally good, although regions close to urbanisation did not comply with standards laid down in the current EC Bathing Water Directive (76/EC/160). Likewise viruses were more commonly, although not exclusively, associated with urban locations, as were phages. Microbial investigation of the sediments confirmed the presence of heterotrophic and oil-oxidising bacteria. Abundance of the latter was closely correlated to the degree of oil contamination of the sediments, and to temperature, although for both, the results showed that the increase in bacterial abundance did level off beyond a certain point. Numbers of oil-oxidising bacteria in the water column displayed a classical response to temperature, with abundance doubling over a 10-degree C rise in temperature. Overall the results suggest that while indices in current use are useful in evaluating coastal quality in the Black Sea, some adjustments would be necessary especially in the establishment of baseline or reference values.     

Effects of fish farm waste on Posidonia oceanica meadows: synthesis and provision of monitoring and management tools

This paper provides a synthesis of the EU project MedVeg addressing the fate of nutrients released from fish farming in the Mediterranean with particular focus on the endemic seagrass Posidonia oceanica habitat. The objectives were to identify the main drivers of seagrass decline linked to fish farming and to provide sensitive indicators of environmental change, which can be used for monitoring purposes. The sedimentation of waste particles in the farm vicinities emerges as the main driver of benthic deterioration, such as accumulation of organic matter, sediment anoxia as well as seagrass decline. The effects of fish farming on P. oceanica meadows are diverse and complex and detected through various metrics and indicators. A safety distance of 400 m is suggested for management of P. oceanica near fish farms followed by establishment of permanent seagrass plots revisited annually for monitoring the health of the meadows.