Simultaneous quantification of dissolved organic carbon fractions and copper complexation using solid-phase extraction

Trace metal cycling in natural waters is highly influenced by the amount and type of dissolved organic C (DOC). Although determining individual species of DOC is unrealistic, there has been success in classifying DOC by determining operationally defined fractions. However, current fractionation schemes do not allow for the simultaneous quantification of associated trace metals. Using operational classifications, a scheme was developed to fractionate DOC based on a set of seven solid-phase extraction (SPE) cartridges. The cartridges isolated fractions based on a range of specific mechanisms thought to be responsible for DOC aggregation in solution, as well as molecular weight. The method was evaluated to determine if it can identify differences in DOC characteristics, including differences in Cu–DOC complexation. Results are that: (1) cartridge blanks were low for both DOC and Cu, (2) differences are observed in the distribution of DOC amongst the fractions from various sources that are consistent with what is known about the DOC materials and the mechanisms operative for each cartridge, (3) when present as a free cation, Cu was not retained by non-cationic cartridges allowing the method to be used to assess Cu binding, (4) the capability of the method to provide quantitative assessment of Cu–DOC complexation was demonstrated for a variety of DOC standards, (5) Cu was found to preferentially bind with high molecular weight fractions of DOC, and (6) estimated partitioning coefficients and conditional binding constants for Cu were similar to those reported elsewhere. The method developed describes DOC characteristics based on specific bonding mechanisms (hydrogen, donor–acceptor, London dispersion, and ionic bonding) while simultaneously quantifying Cu–DOC complexation. The method provides researchers a means of describing not only the extent of DOC complexation but also how that complex will be behave in natural waters.     

Paleo-redox boundaries in fractured granite

At the Earth’s surface, Fe(II) often oxidises and forms insoluble Fe(III)-(oxyhydr)oxides, whose particle size and structure depend on solution composition and temperature during formation and afterwards. Bacterial processes and exposure to reducing environments reduces them again, releasing dissolved iron to the groundwater. During such cycling, the Fe isotopes fractionate to an extent that is expected to depend on temperature. In this study, we report on the use of Fe-oxides as paleo-redox indicators, using their structure, morphology and Fe-composition as a clue for formation conditions. In samples taken from ∼120 m drill cores in granite from SE Sweden, X-ray amorphous, superparamagnetic, nanometre-sized Fe-oxides are confined to fractures of the upper ∼50 m, whereas well-crystalline Fe-oxides, with particle sizes typical for soils, occur down to ∼110 m. We also identified hematite with a particle size of 100 nm, similar to hematite of hydrothermal origin. The Fe isotope composition of the fine-grained Fe-oxides (−1‰ < δ⁵⁶Fe < 1‰, IRMM-14 referenced) scatter significantly compared to the distribution previously observed for hydrothermal material (−0.26‰ < δ⁵⁶Fe < 0.12‰) and they are dominantly heavier than Fe-bearing silicates from fractures (−0.56‰ < δ⁵⁶Fe < −0.35‰). This is consistent with formation by low-temperature weathering, where Fe-silicates dissolve, Fe(II) oxidises and Fe(III)-oxides precipitate. The X-ray amorphous, nanometre-sized nature of near-surface Fe-oxides suggests recent formation. The deeper situated, well-crystalline Fe-oxides are more mature and we interpret that they record earlier oxidising events. They exist in fractures that are not significantly altered, indicating formation during periods of oxidation. Our results show that oxygenated water may reach depths of ∼110 m in fractured granite. The absence of natural, low-temperature Fe-oxides from deeper drill cores suggests that oxygenated waters do not readily penetrate beyond about 100 m and suggests that radioactive waste repositories located at a depth of ∼500 m should be well-protected from oxygenated waters.     

The role of volcanism in the development of the Japan,Okhotsk, and Philippine marginal seas

Newly obtained petrological and geochemical data on Late Mesozoic-Cenozoic volcanic complexes in the Japan, Okhotsk, and Philippine marginal seas of the Pacific Ocean made it possible to specify the types and characteristics of various stages of volcanism in the seas, trace the evolutionary history of the volcanic processes, and identify the geodynamic environments in which the deep-sea basins were formed, as well as to distinguish inherent features in the evolution of marginal seas in the continent-ocean transition zone in the Central Asian sector of the Pacific Ocean. These features imply that the processes that formed this zone in the region were similar. Significant differences revealed between the zones in the region were predetermined, first of all, by the different types of the Earth’s crust that was involved in the major tectonic-magmatic processes and participated in the generation of the magmatic melts.     

Histopathological effects of waterborne silver nanoparticles and silver salt on the gills and liver of goldfish <Emphasis Type="Italic">Carassius</Emphasis><Emphasis Type="Italic">auratus</Emphasis>

This study aimed to compare histopathological effect of waterborne silver nanoparticles and silver salt (AgNO₃) on the gills and liver of Carassius auratus. Therefore, one hundred and five live specimens of goldfish were obtained and treated in five aquariums with 0, 0.01, 0.025, 0.05, and 0.1 ppm of AgNO₃ and 0, 0.1, 0.5, 1, and 5 ppm of Ag nanoparticles (mean particle size of 5 nm). Fish were sampled after 14 days of exposure. Results showed that the kinds of pathologies observed with Ag NPs were broadly of the same type as AgNO₃ including hyperplasia, edema and lifting of the gill epithelium, and lamellar fusion of the gills, and hemosiderosis, hemorrhage, hydropic swelling, and pyknotic nuclei of the liver. Overall, the data showed that although Ag nanoparticles and AgNO₃ pathology were similar, but Ag nanoparticles caused less injury than AgNO₃ in the gills and liver of goldfish. Therefore, it is more proper to use nanoform of Ag in industrials.     

Ecotoxicological evaluation of dredged sediments from Rodrigo de Freitas Lagoon (Rio de Janeiro State,Brazil) using bioassays with earthworms and collembolans

The toxicity and metal bioavailability were studied in dredged sediments from Rodrigo de Freitas Lagoon (Rio de Janeiro, RJ, Brazil) using acute and avoidance tests with Eisenia andrei, and reproduction tests with Folsomia candida. The sediment was mixed with an artificial soil, and two natural soils (ferralsol and chernosol—representative Brazilian tropical soils) to obtain the following doses: 1, 3, 6, 12, 18, 24 and 30%. Total metal concentrations were determined in the sediment to support the interpretation of ecotoxicological data. Metal concentrations in the mixtures were in agreement with the threshold limits established by Brazilian law. However, significant avoidance responses were found on doses ≥?3% and were the most sensitive endpoint. Earthworm mortality found in artificial soil mixtures (LC50?=?3.9) suggests higher toxicity levels than those obtained in ferralsol (LC50?=?7.6%) and chernosol (11.0%) treatments. Earthworm mortality, avoidance responses and collembolan reproduction levels found in ferralsol mixtures (LC50?=?9.2; avoidance EC50?=?2.3%; reproduction EC50?=?2.8%) were higher compared to chernosol treatments (LC50?=?11.0%; avoidance EC50?=?4.3%; reproduction EC50?=?4.9%). The reduction of toxicity levels in chernosol mixtures is probably due to the abundance of expansive clay minerals in chernosols with capacity of adsorbing metals and other xenobiotic substances from soil pore water, decreasing metal bioavailability. Finally, threshold limits defined by Brazilian legislation for soil quality and land disposal of dredged sediments are not sufficient to prevent noxious effects on soil fauna and should be complemented with a preliminary ecotoxicological evaluation.     

Tectonic framework of the Precambrian of Madagascar and its Gondwana connections: a review and reappraisal

The Precambrian of Madagascar is divided into two sectors by the north-west trending sinistral Ranotsara shear zone, which continues in the Mozambique belt, probably as the Surma shear zone, and in Southern India as the Achankovil shear zone. South of Ranotsara six north-south trending tectonic belts are recognized that consist largely of granulite and high amphibolite facies paragneisses, phlogopite diopsidites, concordant granites and granulites. North of Ranotsara the central-northern segment is traversed by a north-trending axial 100–150 km wide dextral shear zone of probable Pan-African age, which was metamorphosed under granulite and high amphibolite facies conditions and which has reworked older basement. This shear zone continues across southern India as the Palghat-Cauvery shear zone. Major stratiform basic -ultrabasic complexes occur in the axial zone and in the basement to the west. Well preserved low grade continental margin-type sediments (quartzites, mica schists and stromatolitic marbles) of Kibaran age are present in western Madagascar. Two partly greenschist grade sedimentary groups lie unconformably on high grade basement in north-east Madagascar. Isotopic age data suggest the presence in Madagascar of Archaean, Early and Mid-Proterozoic crustal material that was extensively reworked in Pan-African times.     

Soil characteristics and nutrient status in a Northern Australian mangrove forest

The results of a study of soil factors in relation to plant growth for a tropical mangrove forest in northern Australia are presented and discussed. Basic soil properties are described briefly in terms of particle size distribution, bulk density and total carbon, nitrogen and phosphorus. Soil redox potential, pH, salinity and extractable nitrogen and phosphorus were monitored monthly over a 14 month period commencing April 1979. Sampling was carried out at 9 sites along a 370 m transect which exhibits strong gradients in topography, above ground biomass, canopy height and species distribution. Statistical analysis of the data shows that above ground biomass correlates significantly with the following soil factors, averaged over depth within the rooting zone and over time: Extractable P (r=0.85, p<0.01), redox potential (r=0.89, p<0.01) and salinity (r=?0.79, p<0.05). The strong biomass-E_H correlation may be partly due to oxygen translocation by the plants to the root zone. Soil ammonium levels were within the range of 1–14 μg N per g (dry wt) and, unlike the above parameters, showed only minor variation with position along the transect. Variation of ammonium levels with time was apparent, but no significant correlation with rate of new shoot growth could be demonstrated, although depth profiles indicated depletion of ammonium by plant uptake during rapid growth periods. In addition neither soil ammonium, extractable phosphorus nor rate of plant growth showed any definite seasonal periodicity in this tropical system.     

Structural investigations of Australian coals—I. A characterization of Victorian brown coal lithotypes and their kerogen and humic acid fractions by i.r. spectroscopy

The functional groups of brown coal lithotypes, their humic acids and kerogens were investigated by elemental analysis and quantitative infrared spectroscopy using absorption coefficients.An inverse relationship is reported between the concentrations of kerogen and humic acids for each lithotype and significant variation in the levels of humic acids with lithotype are attributed to changing higher plant input and depositional environments.The structural implications of observed trends in absorption coefficients and their usefulness as a rapid method of functional group analysis has been investigated. Using this infrared technique, kerogen structures as reflected in functional group analyses were found to exhibit a dependance on lithotype, although no significant variation in the functionality of the humic acid structures was observed.     

Background of ground penetrating radar measurements

Characterization of the shallow subsurface (0.25 to 10 m) is of growing importance for engineering activities, solutions of environmental problems, and archaeological investigations. Ground-penetrating radar (GPR) is an appropriate technique considering the depth range of interest, the strength of electric and magnetic contrasts between different subsurface layers and buried objects, and the required resolution. GPR surveys can detect subsurface structures by recording electromagnetic reflections from discontinuities. The detectability of objects and the delineation of subsurface structures increases with increasing wave velocity and conductivity differences between the object and its surroundings or between adjacent layers. However, unwanted reflections from objects above the surface influence the images. Shielded antennas can be used to avoid strong reflections from these objects. The data thus obtained are, however, more difficult to interpret. The fundamentals of GPR and two different acquisition setups for a GPR system are discussed. Basic interpretation tools for travel-time and velocity estimation are described, and finally, case studies are presented, followed by conclusions.