Manganese oxide minerals: Crystal structures and economic and environmental significance

Manganese oxide minerals have been used for thousands of years—by the ancients for pigments and to clarify glass, and today as ores of Mn metal, catalysts, and battery material. More than 30 Mn oxide minerals occur in a wide variety of geological settings. They are major components of Mn nodules that pave huge areas of the ocean floor and bottoms of many fresh-water lakes. Mn oxide minerals are ubiquitous in soils and sediments and participate in a variety of chemical reactions that affect groundwater and bulk soil composition. Their typical occurrence as fine-grained mixtures makes it difficult to study their atomic structures and crystal chemistries. In recent years, however, investigations using transmission electron microscopy and powder x-ray and neutron diffraction methods have provided important new insights into the structures and properties of these materials. The crystal structures for todorokite and birnessite, two of the more common Mn oxide minerals in terrestrial deposits and ocean nodules, were determined by using powder x-ray diffraction data and the Rietveld refinement method. Because of the large tunnels in todorokite and related structures there is considerable interest in the use of these materials and synthetic analogues as catalysts and cation exchange agents. Birnessite-group minerals have layer structures and readily undergo oxidation reduction and cation-exchange reactions and play a major role in controlling groundwater chemistry.

Competitividade da cadeia produtiva do Arapaima gigas, o pirarucu da Amazônia brasileira

Com um quinto da água doce do planeta, o sistema fluvial da Amazônia apresenta um enorme potencial para piscicultura. De acordo com a FAO, em função das suas condições geográficas, o Brasil é um dos poucos países que tem condições de atender à crescente demanda mundial, podendo tornar-se um dos maiores produtores de peixes do mundo. A observação desse potencial amazônico motivou o desenvolvimento desta pesquisa que se debruça sobre a questão da competitividade da cadeia produtiva de Arapaima gigas, o pirarucu da Amazônia brasileira. As pesquisas de campo levaram ao mapeamento de duas cadeias: a cadeia extrativista e a piscicultura. A abordagem sistêmica permitiu a verificação das características dos atores e as bases sob as quais as transações se estabelecem. À luz da teoria das restrições foram identificados os gargalos que impedem a competitividade do sistema, inclusive alertando para os recursos com restrição de capacidade. Comprovou-se que a falta de uma cadeia produtiva devidamente organizada pode provocar graves prejuízos a determinados elos, enquanto outros membros aproveitam-se de ações oportunistas para ampliar suas margens de lucro. Da mesma forma, a ausência de uma cadeia produtiva completa impede a fixação do valor gerado na região de origem das matérias-primas. No entanto, também foi possível comprovar que há possibilidade de desenvolver o extrativismo atribuindo valor econômico aos recursos naturais e gerando renda para a comunidade local. Além de apresentar o panorama do setor na região delimitada, este estudo culminou em reflexões capazes de orientar políticas públicas para o desenvolvimento de cadeias produtivas completas na região da Amazônia brasileira.

Análise de conflitos de usos múltiplos da água auxiliada por simulação computacional: bacia do rio Sapucaí - Mirim/Grande

Na mesma proporção que fontes de água potável são reduzidas, a competição por elas tem aumentado, conseqüência imediata da expansão de áreas urbanas e de novas demandas agro-industriais. Os conflitos gerados por esta competição tendem a comprometer o desenvolvimento sustentável e o progresso de uma forma geral, uma vez que resultam em perda de eficácia para vultuosos investimentos públicos e privados e em prejuízos para os usuários menos estruturados. Considerando os fatos acima, o objeto deste trabalho é o estabelecimento de cenários de alocação das disponibilidades hídricas entre usuários de água da bacia do Sapucaí-Mirim/Grande, visando determinar a convivência harmoniosa das várias finalidades de uso provenientes do mesmo recurso hídrico. Tal meta poderá ser alcançada através da análise dos indicadores de desempenho - confiabilidade, vulnerabilidade e resiliência - do sistema os quais serão obtidos com o auxílio do modelo de simulação IRAS (Interactive River Aquifer Simulation).

Applying reactive models to column experiments to assess the hydrogeochemistry of seawater intrusion: optimising ACUAINTRUSION and selecting cation exchange coefficients with PHREEQC

Three sets of laboratory column experimental results concerning the hydrogeochemistry of seawater intrusion have been modelled using two codes: ACUAINTRUSION (Chemical Engineering Department, University of Alicante) and PHREEQC (U.S.G.S.). These reactive models utilise the hydrodynamic parameters determined using the ACUAINTRUSION TRANSPORT software and fit the chloride breakthrough curves perfectly. The ACUAINTRUSION code was improved, and the instabilities were studied relative to the discretisation. The relative square errors were obtained using different combinations of the spatial and temporal steps: the global error for the total experimental data and the partial error for each element. Good simulations for the three experiments were obtained using the ACUAINTRUSION software with slight variations in the selectivity coefficients for both sediments determined in batch experiments with fresh water. The cation exchange parameters included in ACUAINTRUSION are those reported by the Gapon convention with modified exponents for the Ca/Mg exchange. PHREEQC simulations performed using the Gains-Thomas convention were unsatisfactory, with the exchange coefficients from the database of PHREEQC (or range), but those determined with fresh water – natural sediment allowed only an approximation to be obtained. For the treated sediment, the adjusted exchange coefficients were determined to improve the simulation and are vastly different from those from the database of PHREEQC or batch experiment values; however, these values fall in an order similar to the others determined under dynamic conditions. Different cation concentrations were simulated using two different software packages; this disparity could be attributed to the defined selectivity coefficients that affect the gypsum equilibrium. Consequently, different calculated sulphate concentrations are obtained using each type of software; a smaller mismatch was predicted using ACUAINTRUSION. In general, the presented simulations by ACUAINTRUSION and PHREEQC produced similar results, making predictions consistent with the experimental data. However, the simulated results are not identical to the experimental data; sulphate (total S) is overpredicted by both models, most likely due to such factors as the kinetics of gypsum, the possible variations in the exchange coefficients due to salinity and the neglect of other processes.

Optimal Design of a Hybrid Membrane System Combining Reverse and Forward Osmosis for Seawater Desalination

In this work we study Forward Osmosis (FO) as an emerging desalination technology, and its capability to replace totally or partially Reverse Osmosis (RO) in order to reduce the great amount of energy required in the current desalination plants. For this purpose, we propose a superstructure that includes both membrane based desalination technologies, allowing the selection of only one of the technologies or a combination of both of them seeking for the optimal configuration of the network. The optimization problem is solved for a seawater desalination plant with a given fresh water production. The results obtained show that the optimal solution combines both desalination technologies to reduce not only the energy consumption but also the total cost of the desalination process in comparison with the same plant but operating only with RO.

Geochemistry of sediments of stage 5 of the Nordic seas

Stable isotope, foraminifera and ice rafted detritus (IRD) records covering the last interglacial (the Eemian) from 7 sediment cores in a transect from the Norwegian to the Greenland Sea are presented. The percentages of Neogloboquadrina pachyderma (s.) and Globigerina quinqueloba, foraminiferal content, and to some extent planktonic stable isotope records, demonstrate marked, regional changes in surface water conditions. Importantly, the variability in the abundances of subpolar foraminifera and foraminiferal content are not coherent, implying that these two types of proxies fluctuated independently of each other and most likely reflect changes in sea surface temperature and surface water carbonate productivity, respectively. Paleoceanographic reconstructions demonstrate significant movements of the oceanographic fronts. At the warmest periods, the Arctic front was located far west of the present-day location, at least within the Iceland Sea region. At 126-125 ka, this was most probably due to a stronger or more westerly located Norwegian current. Within the later warm intervals, higher heat flux to the western part of the basin reflects a combination of a stronger Irminger current and/or a weaker east Greenland current. During the main cold spell at ~124 ka, a diffuse Arctic front had a more southeasterly location than today, and intrusion of Atlantic surface waters was probably limited to a narrow corridor in the Eastern Norwegian Sea. A general correspondence between minima in sea surface temperatures and light benthic delta18O may indicate enhanced influx of freshwater to the basin within the cold events. At least in the Norwegian Sea, we find some evidence that the changes in surface water conditions are associated with changes in deep water ventilation. The majority of the fluctuations may be related to occasional breakdown or reduction of the thermohaline circulation within the Nordic seas. In the earliest Eemian, this could result from meltwater forcing. During the remaining part of the last interglacial the fine balance between temperature and salinity, which the deep water formation is depending on, may have been disturbed by periodic increases in fresh water supply or variable influx of warm Atlantic surface waters.

(Table 2) Trace metal concentrations in ODP Hole 169-1033B

We measured the concentrations of redox-sensitive trace metals (Mn, V, Mo, U, Cd and Re) in sediments from ODP Leg 169S Hole 1033B in Saanich Inlet, British Columbia, to determine changes in redox conditions associated with the onset of laminated sediments at ~12.5 kyr. The most striking result is a large peak in authigenic Re along with detrital levels of Mo at the glacial terrigenous clay-diatomaceous sediment transition. In contrast, the underlying glacial terrigenous clay, which extends throughout the bottom section of the core, is chemically similar to detrital concentrations, either Cowichan River particulates or average shale values. These data suggest a period of oxic bottom waters but reducing pore-waters. This could be due to the dramatic transformation of Saanich Inlet during the late deglaciation from an open bay to an inlet, which restricted circulation and slowed bottom water oxygen renewal. A peak and gradual increase in authigenic Mn in younger sediments subsequent to the Re peak suggests that increasingly oxic conditions followed the authigenic enrichment in Re. These conditions could be connected to the Younger Dryas cooling period, which was coincident with an increase in well oxygenated upwelled waters on the west coast of North America that form the bottom waters of Saanich Inlet. Metal concentrations in a gray clay bed (~11 kyr) are similar to their concentrations in the glacial terrigenous clay, implying that they have a common source. Authigenic enrichments of Re with little authigenic Mo and Cd suggest that before the deposition of this bed, bottom waters were oxic and pore-water oxygen was consumed in the top centimeter or less. Laminations above the clay layer suggest anoxic conditions, which are also indicated by higher authigenic Mo and Cd and slightly lower Re/Mo ratios in these sediments. The basin remained mostly anoxic after the gray clay was emplaced, as seen by continuous authigenic enrichment of the redox-sensitive trace metals. These results are consistent with increased stratification of the water column, brought about by an influx of fresh water to the basin by a large flood.

Sedimentological investigations and age model on sediment core PS2561-2

Benthic d13C values (F. wuellerstorfi), kaolinite/chlorite ratios and sortable silt median grain sizes in sediments of a core from the abyssal Agulhas Basin record the varying impact of North Atlantic Deep Water (NADW) and Antarctic Bottom Water (AABW) during the last 200 ka. The data indicate that NADW influence decreased during glacials and increased during interglacials, in concert with the global climatic changes of the late Quaternary. In contrast, AABW displays a much more complex behaviour. Two independent modes of deep-water formation contributed to the AABW production in the Weddell Sea: 1) brine rejection during sea ice formation in polynyas and in the sea ice zone (Polynya Mode) and 2) super-cooling of Ice Shelf Water (ISW) beneath the Antarctic ice shelves (Ice Shelf Mode). Varying contributions of the two modes lead to a high millennial-scale variability of AABW production and export to the Agulhas Basin. Highest rates of AABW production occur during early glacials when increased sea ice formation and an active ISW production formed substantial amounts of deep water. Once full glacial conditions were reached and the Antarctic ice sheet grounded on the shelf, ISW production shut down and only brine rejection generated moderate amounts of deep water. AABW production rates dropped to an absolute minimum during Terminations I and II and the Marine Isotope Transition (MIS) 4/3 transition. Reduced sea ice formation concurrent with an enhanced fresh water influx from melting ice lowered the density of the surface water in the Weddell Sea, thus further reducing deep water formation via brine rejection, while the ISW formation was not yet operating again. During interglacials and the moderate interglacial MIS 3 both brine formation and ISW production were operating, contributing various amounts to AABW formation in the Weddell Sea.

Tidal and spatial variations of DI13C and aquatic chemistry in a temperate tidal basin during winter time

Here, the pelagic carbonate system and the ?13C signature of dissolved inorganic carbonate (DIC) were investigated in a tidal basin of the southern North Sea, the Jade Bay, with respect to tidal cycles and a transect towards the North Sea in winter time (January and November, 2010). Physical parameters, major and trace elements, and nutrient concentrations were considered, too. Primary production and pelagic organic matter respiration were negligible during winter time. Both, the compositional variations on the transects as well as during the tidal cycles indicate the mixing of North Sea with fresh water. The combined spatial co-variations of different parameters indicate an introduction of fresh water that was enriched in DI12C, metabolites (e.g., ammonia), protons, and dissolved redox-sensitive elements (e.g., Mn2+). During the January campaign, the discharge via the flood gates was limited due to ice cover of the hinterland drainage ditches, allowing for an observation of tidal variations without significant mixing contributions from surface water discharges. Considering a binary mixing model with North Sea and fresh water as end-members, the extrapolated fresh water end-member composition for this campaign is estimated to contain about 3.8 mmol/kg DIC , and enhanced concentrations of NH4+, Mn2+, and protons compared to North Sea water. The fast temporal response of dissolved geochemical tracers on tidal variations in the Jade Bay indicates a continuous supply of a fresh water component. The measured composition of fresh waters entering the Jade Bay via flood gates (end of October, 2010) did not match the values estimated by the binary mixing model. Therefore, the overall fresh water component likely is a mixture between sources originating from flood gates and (in January) dominating submarine groundwater discharge entering the Jade Bay. This model is consistent with the results obtained during the November campaign, when a more important contribution from flood gates is expected and a more variable fresh water end-member is estimated. The co-variations of the concentrations and the stable carbon isotope composition of DIC are applied to evaluate possible superimposed sink-source-transformation processes in the coastal waters and a general co-variation scheme is suggested.

Zooplankton abundance and vertical fluxes of sedimentary matter and chemical elements in the White Sea from 15 to 24 June, 2000

A multidisciplinary oceanographic survey of the White Sea was carried out in the Gorlo Straight, Basin, and Kandalaksha Bay regions including estuaries of Niva, Kolvitza and Knyazhaya rivers. Hydrophysical study in the northern part of the Basin revealed long-lived step-like structures and inversions in vertical profiles of temperature and salinity, which formed due to tidal mixing of saline and cold Barents Sea waters and warmer White Sea waters in the Gorlo Straight. Biological studies revealed the main features of spatial distribution, as well as qualitative and quantitative composition of phyto- and zooplankton in all studied areas; tolerance of main zooplankton species to fresh water influence in estuaries was shown. Study of suspended matter in estuaries clearly demonstrated physicochemical transformations of material supplied by the rivers. Data on vertical particle flux in the deep part of the Kandalaksha Bay showed difference between the upper and near-bottom layers, which could result from sinking of spring phytoplankton bloom products and supply of terrigenic suspended matter from the nepheloid layer formed by tidal currents.

The interstitial subsoil fauna on the beach of Sarso Island, Red Sea

The scope of this research was to find out, how important is the presence of brackish water for the formation of the characteristical littoral subsoil fauna in the interstitial spaces of beaches. There is little precipitation in the Red Sea area and therefore little influence of freshwater on the beach. Moreover, the sandy beach of Sarso Island (Farasan Archipelago) is bordered landwards and underneath by solid limestone, preventing subsoil fresh water, if there is any, from penetrating into the beach region. The salinity of the interstitial water from Sarso beach lies a little above the salinity of the adjacent sea. The microfauna of Sarso beach is composed to a rather big proportion of such species that are known to be characteristical littoral subsoil water species, partially of world wide distribution. The ecological analysis of this fauna, i.e. the freeliving Nematodes, reveals the presence of two distinct associations: 1. the association of the low level subsoil region, close to the sea, with clear interstitial water, subject to regular exchange with the water of the adjcent sea. 2. the association of the high level subsoil region, 4-10 meter distant from the sea, with brownish water. Contrary to earlier results there is no distinction in salinity between the two associations, so it is not longer justified to apply the term brackish water fauna on the animals living in the association of the high level subsoil region.