Numerical solution of nonlinear equations in chemical speciation calculations

Speciation calculations involve the computation of the concentration of each individual chemical species in a multicomponent–multiphase chemical system. The numerical problem is to solve a system of coupled linear and nonlinear equations subject to the constraint that all unknowns are positive. The performance and accuracy of a series of nonlinear equation solvers are evaluated: A quasi-Newton method with the global step determined by different line search and trust region algorithms, the conjugate gradient method with the global step determined by line search, and the solvers in the codes TENSOLVE, CONMIN and LBFGS.     

Polychlorinated biphenyls (PCB) and organochlorine pesticides in sediments of the baltic and coastal waters of Mecklenburg-Vorpommern

Summary The distribution of polychlorinated biphenyls (PCB) and organochlorine pesticides, e.g. the isomers of hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), p,p’-dichiorodiphenyitrichloroethane (DDT) and its primary metabolites DDE and DDD was investigated in surface sediments (0–2 cm) and sediment cores (0–45 cm) from the western Baltic Sea and the coastal waters of Mecklenburg-Vorpommern. Sediment sampling was carried out in the Belt Sea, the Arkona Basin, the Pomeranian Bight and in almost all Bodden and Haff areas of Mecklenburg-Vorpommern in autumn 1993 and 1994. The highest concentrations of PCB and DDT compounds, measured in the innercoastal waters, reached 214 ng g^-1 dry weight (d. w.). The values of HCH isomers ranged between 0.01 and 2.9 ng g^-1 d.w., the highest levels being those of Β-HCH. Levels of chlorinated hydrocarbons, which varied depending on the sediment properties, indicated increased riverine inputs (Oder, Peene, and Uecker). Elevated levels in the Oderhaff and Peenestrom characterize that area as a sink and, due to remobilization of the upper sediment layer (fluffy layer) into the pelagic, also as a source of organic contaminants. Input from agriculture and industrial point sources (shipyards, shipbuilding) was observed in the coastal waters. The homogeneous PCB and DDT distribution (TOC standardization) observed in the surface sediments of some areas in the western Baltic indicates high sediment dynamics. This is supported by the results of sediment core analyses which showed a constant PCB and DDT distribution down to a depth of 15 to 20 cm.

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Polychlorierte Biphenyle (PCB) und Organochlorpestizide im Sediment der Ostsee und der Küsten-gew?sser Mecklenburg-Vorpommerns

Zusammenfassung Die Verteilungen von polychlorierten Biphenylen (PCB) und Organochlorpestiziden (DDT, HCH und HCB) wurden in Oberfl?chensedimenten (0–2 cm) und in Sedimentkernen (0–45 cm) der westlichen Ostsee und der Küstengew?sser Mecklenburg-Vorpommerns untersucht. Die Sedimentprobenahme erfolgte in der Beltsee, der Arkonasee, der Pommerschen Bucht und in nahezu allen Bodden-und Haffgew?ssern Mecklenburg-Vorpommerns im Herbst 1994 und 1995. Die h?chsten Konzentrationen wurden für die PCB-und DDT-Verbindungen bis 214 ng g^-1 Trockenmasse (TM) in den Küstengew?ssern gemessen. Für die HCH-Isomeren lagen die Werte zwischen 0,01 und 2,9 ng g^-1 TM, mit h?chsten Konzentrationen für das Β-HCH. Die Werte der chlorierten Kohlenwasserstoffe (CKW) variieren nach der Sedimentbeschaffenheit und weisen auf erh?hte Eintr?ge über die Flu\systeme (Oder und Peene) hin. Die h?heren Konzentrationen in den Bodden-und Haffgew?ssern charakterisieren diese Gebiete als Senke und durch erneute Mobilisierung der oberen Sedimentschicht in das Pelagial auch als Quelle für die organischen Schadstoffe. Insbesondere konnten die Eintr?ge aus der Landwirtschaft und aus industriellen Punktquellen (Werftstandorte, Schiffbau) in den Küstengew?ssern festgestellt werden. Die nahezu homogene PCB-und DDT-Verteilung im Oberfl?chensediment der westlichen Ostsee ist ein Hinweis auf die hohe Sedimentdynamik in diesem Gebiet. Dieses wird durch die Ergebnisse der Untersuchungen an Sedimentkernen unterstützt, die eine konstante PCB-und DDT-Verteilung bis zu einer Tiefe von 15 bis 20 cm zeigten.

     

Acceleration Phase of Coronal Mass Ejections: I. Temporal and Spatial Scales

We study kinematics of 22 coronal mass ejections (CMEs) whose motion was traced from the gradual pre-acceleration phase up to the post-acceleration stage. The peak accelerations in the studied sample range from 40, up to 7000 m s⁻², and are inversely proportional to the acceleration phase duration and the height range involved. Accelerations and velocities are, on average, larger in CMEs launched from a compact source region. The acceleration phase duration is proportional to the source region dimensions; i.e., compact CMEs are accelerated more impulsively. Such behavior is interpreted as a consequence of stronger Lorentz force and shorter Alfvén time scales involved in compact CMEs (with stronger magnetic field and larger Alfvén speed being involved at lower heights). CMEs with larger accelerations and velocities are on average wider, whereas the widths are not related to the source region dimensions. Such behavior is explained in terms of the field pile-up ahead of the erupting structure, which is more effective in the case of a strongly accelerated structure.     

Sources of dissolved silica to the fjords of northern Patagonia (44–48°S): the importance of volcanic ash soil distribution and weathering

Dissolved silica (DSi) plays an important biogeochemical role in the fjords of northern Chilean Patagonia (44–48°S), where it drives high biogenic productivity and promotes carbon burial. It is generally believed that the DSi riverine input to lakes and coastal environments is controlled by a combination of factors including lithology, climate, topography, vegetation, and meltwater input. In northern Chilean Patagonia several authors have proposed that the postglacial volcanic ash soils (andosols) may play a significant role in the high supply of DSi to the regional fjords. To assess the influence of andosols on DSi concentrations in north Patagonian rivers, we mapped andosol thickness and compared our results with river chemistry. The mineralogical and geochemical composition of three representative andosol profiles was also examined to evaluate the efficiency of weathering processes. The andosol thickness map clearly demonstrates that volcanic ash was predominantly deposited on the eastern side of the regional volcanoes, reflecting the influence of the prevailing westerly winds on the distribution of pyroclastic material. Mineralogical and geochemical results show that the andosol parent material has the typical andesitic basaltic signature of the regional volcanoes, i.e. high amounts of amorphous material, plagioclase, K‐feldspar, and pyroxene. Down‐profile variations in soil mineralogy and geochemistry indicate increased leaching of silica with depth, resulting from weathering of the volcanic parent material. For the five studied watersheds, a highly positive correlation (R²=0.98) was found between average andosol thickness and DSi concentrations, suggesting that andosol thickness is the main parameter affecting DSi concentrations in north Patagonian river systems. On seasonal timescales, increased precipitation (winter) and glacial meltwater (summer) input can significantly reduce DSi concentrations. We argue that the weathering of andosols constitutes the most important source of DSi to the lakes and fjords of northern Chilean Patagonia, explaining the particularly high regional rates of biogenic silica production. Copyright © 2015 John Wiley & Sons, Ltd.     

Demographic and environmental conditions are uncoupled in the social–ecological system of the Pribilof Islands

Since the end of the commercial fur seal hunt in 1984, the economy of the Pribilof Islands, Alaska, has lacked a stable, lasting basis. As a contribution to the effort to understand and promote the effective management of the Pribilof Islands as a social–ecological system, we examined current and recent conditions on the islands to assess local perceptions of, and prospects for, economic, social and environmental well-being. We found few correlations between environmental conditions and socio-economic indicators. The lack of apparent connection between population levels and economic or environmental stimuli is likely attributable to one or more of several factors: (a) modest economic dependence on the environment; (b) predominance of other economic inputs to the economies of the islands; (c) islanders basing residence choices largely on non-economic factors; and (d) the islanders' tolerance for economic fluctuations and uncertainty. These results suggest economic analysis alone is insufficient to explain the dynamics of this social–ecological system, contrary to many other case studies and an expectation of tight coupling and clear connections between society and ecology in the Pribilofs.     

Effects of an Acute Hypoxic Event on Microplankton Community Structure in a Coastal Harbor of Southern California

Fish mortality and hypoxic events occur in many coastal and inland systems and may result from natural or anthropogenically mediated processes. The effects of consequent changes in water biogeochemistry have been investigated for communities of benthic invertebrates and pelagic metazoans. The responses of micro-plankton assemblages, however, have remained largely unstudied. The northern basin of King Harbor, a small embayment within Santa Monica Bay, CA, USA, suffered a massive fish kill in March 2011 as a consequence of acute hypoxia. Dissolved oxygen concentrations < 0.1 ml?l^?1 were measured in the northern basin of the harbor for several days following the mortality event, and a strong spatial gradient of oxygen was observed from the northern basin to waters outside the harbor. The microplankton community within King Harbor differed significantly from a diatom-dominated community present in neighboring Santa Monica Bay. The latter region appeared unaffected by physicochemical changes, induced by the fish kill, that were observed within the harbor. A trophic shift was observed throughout King Harbor from a photoautotrophic-dominated assemblage to one of heterotrophic forms, with relative abundances of bacterivorous ciliates increasing by more than 80 % in the most impacted part of the harbor. Significant changes in community structure were observed together with dramatically reduced photosynthetic yield of the remaining phytoplankton, indicating severe physiological stress during the extreme hypoxia.     

The last glaciation of the Arctic volcanic island Jan Mayen

The volcanic island of Jan Mayen, remotely located in the Norwegian-Greenland Sea, was covered by a contiguous ice cap during the Late Weichselian. Until now, it has been disputed whether parts of the island south of the presently glaciated Mount Beerenberg area were ever glaciated. Based on extensive field mapping we demonstrate that an ice cap covered all land areas and likely also extended onto the shallow shelf areas southeast and east of the island. Chronological interpretations are based on K-Ar and ⁴⁰Ar/³⁹Ar dating of volcanic rocks, cosmogenic nuclide (³⁶Cl) surface exposure dating of bedrock and glacial erratics, and radiocarbon dating. We argue that ice growth started after 34 ka and that an initial deglaciation started some 21.5–19.5 ka in the southern and middle parts of the island. In the northern parts, closer to the present glaciers, the deglaciation might have started later, as evidenced by the establishment of vegetation 17–16 cal. ka BP. During full glaciation, the ice cap was likely thickest over the southern part of the island. This may explain a seemingly delayed deglaciation compared with the northern parts despite earlier initial deglaciation. In a broader context, the new knowledge of the Late Weichselian of the island contributes to the understanding of glaciations surrounding the North Atlantic and its climate history.     

Dynamics of xenobiotic transformation processes in soil systems: A zero-dimensional system model applied to ethylenethiourea

A zero-dimensional model for the environmental fate of ethylenethiourea (ETU) in soils was formulated. The relevant physicochemical transformation processes were derived from published data, and their dynamics analyzed. Corresponding kinetic submodels for sorption, photodegradation, abiotic oxidation and biodegradation were then developed based on assumptions on the dominant process mechanisms. These submodels, and the overall model of biotic degradation in soil, were applied to literature data with determination coefficients of R² > 0.9, validating the assumed process dynamics.