Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.     

Explicit stress–strain equations for modeling frictional materials

In this paper, a comprehensive study on simulating the shearing behavior of frictional materials is performed. A set of two explicit equations, describing the relationship among the shear stress ratio and the distortional strain and the volumetric strain, are formulated independently. The equations contain three stress parameters and three strain parameters and another parameter representing the nonuniformity of stress and strain during softening. All the parameters have clear physical significance and can be determined experimentally. It is demonstrated that the proposed equations have the capacity of simulating the complicated shearing behavior of many types of frictional materials including geomaterials. The proposed equations are used to simulate the stress–strain behavior for 27 frictional materials with 98 tests. These materials include soft and stiff clays in both reconstituted and structured states, silicon sands and calcareous sands, silts, compacted fill materials, volcanic soils, decomposed granite soils, cemented soils (both artificially and naturally cemented), partially saturated soils, ballast, rocks, reinforced soils, tire chips, sugar, wheat, and rapeseed. It has been demonstrated that the proposed explicit constitutive equations have the capacity to capture accurately the shearing behavior of frictional materials both qualitatively and quantitatively. A study on model parameters has been performed.     

Leachable particulate iron in the Columbia River,estuary, and near-field plume

This study examines the distribution of leachable particulate iron (Fe) in the Columbia River, estuary, and near-field plume. Surface samples were collected during late spring and summer of 2004–2006 as part of four River Influence on Shelf Ecosystems (RISE) cruises. Tidal amplitude and river flow are the primary factors influencing the estuary leachable particulate Fe concentrations, with greater values during high flow and/or spring tides. Near the mouth of the estuary, leachable particulate Fe [defined as the particulate Fe solubilized with a 25% acetic acid (pH 2) leach containing a weak reducing agent to reduce Fe oxyhydroxides and a short heating step to access intracellular Fe] averaged 770 nM during either spring tide or high flow, compared to 320 nM during neap tide, low flow conditions. In the near-field Columbia River plume, elevated leachable particulate Fe concentrations occur during spring tides and/or higher river flow, with resuspended shelf sediment as an additional source to the plume during periods of coastal upwelling and spring tides. Near-field plume concentrations of leachable particulate Fe (at a salinity of 20) averaged 660 nM during either spring tide or high flow, compared to 300 nM during neap tide, low flow conditions. Regardless of tidal amplitude and river flow, leachable particulate Fe concentrations in both the river/estuary and near-field plume are consistently one to two orders of magnitude greater than dissolved Fe concentrations. The Columbia River is an important source of reactive Fe to the productive coastal waters off Oregon and Washington, and leachable particulate Fe is available for solubilization following biological drawdown of the dissolved phase. Elevated leachable Fe concentrations allow coastal waters influenced by the Columbia River plume to remain Fe-replete and support phytoplankton production during the spring and summer seasons.     

Coupled finite‐element simulation of injection well testing in unconsolidated oil sands reservoir

This paper presents a finite‐element (FE) model for simulating injection well testing in unconsolidated oil sands reservoir. In injection well testing, the bottom‐hole pressure (BHP) is monitored during the injection and shut‐in period. The flow characteristics of a reservoir can be determined from transient BHP data using conventional reservoir or well‐testing analysis. However, conventional reservoir or well‐testing analysis does not consider geomechanics coupling effects. This simplified assumption has limitations when applied to unconsolidated (uncemented) oil sands reservoirs because oil sands deform and dilate subjected to pressure variation. In addition, hydraulic fracturing may occur in unconsolidated oil sands when high water injection rate is used. This research is motivated in numerical modeling of injection well testing in unconsolidated oil sands reservoir considering the geomechanics coupling effects including hydraulic fracturing. To simulate the strong anisotropy in mechanical and hydraulic behaviour of unconsolidated oil sands induced by fluid injection in injection well testing, a nonlinear stress‐dependent poro‐elasto‐plastic constitutive model together with a strain‐induced anisotropic permeability model are formulated and implemented into a 3D FE simulator. The 3D FE model is used to history match the BHP response measured from an injection well in an oil sands reservoir. Copyright © 2013 John Wiley & Sons, Ltd.     

Computational homogenization of uncoupled consolidation in micro‐heterogeneous porous media

Variationally consistent homogenization is exploited for the analysis of transient uncoupled consolidation in micro‐heterogeneous porous solids, whereby the classical approach of first‐order homogenization for stationary problems is extended to transient problems. Homogenization is then carried out in the spatial domain on representative volume elements (RVE), which are introduced in quadrature points in standard fashion. Along with the classical averages, a higher‐order conservation quantity is obtained. An iterative FE²‐algorithm is devised for the case of nonlinear permeability and storage coefficients, and it is applied to pore pressure changes in asphalt‐concrete (particle composite). Various parametric studies are carried out, in particular, with respect to the influence of the ‘substructure length scale’ that is represented by the size of the RVE's. Copyright © 2009 John Wiley & Sons, Ltd.     

Process length variation of the cyst of the dinoflagellate Protoceratium reticulatum in the North Pacific and Baltic‐Skagerrak region: calibration as an annual density proxy and first evidence of pseudo‐cryptic speciation

Process length variation of cysts of the dinoflagellate Protoceratium reticulatum (Claparède et Lachmann) Bütschli in surface sediments from the North Pacific was investigated. The average process length showed a significant inverse relation to annual seawater density: σ_{t annual} = ?0.8674 × average process length + 1029.3 (R² = 0.84), with a standard error of 0.78 kg m^?3. A sediment trap study from Effingham Inlet in British Columbia revealed the same relationship between average process length and local seawater density variations. In the Baltic–Skagerrak region, the average process length variation was related significantly to annual seawater density: σ_{t annual} = 3.5457 × average process length ? 993.28 (R² = 0.86), with a standard error of 3.09 kg m^?3. These calibrations cannot be reconciled, which accentuates the regional character of the calibrations. This can be related to variations in molecular data (small subunit, long subunit and internal transcribed spacer sequences), which show the presence of several genotypes and the occurrence of pseudo‐cryptic speciation within this species. Copyright © 2012 John Wiley & Sons, Ltd.     

Stability of the assemblage albite plus forsterite at high temperatures and pressures with petrologic implications

The maximum limits of the assemblage albiteforsterite have been determined experimentally at high pressures and temperatures. At subsolidus temperatures, albite plus forsterite is replaced at high pressures by jadeitic clinopyroxene and enstatitic orthopyroxene. The boundary for this reaction lies within experimental uncertainity of that for jadeite=albite+nepheline. Melting of albite+forsterite at high pressures produces enstatite+liquid, which is different from the low-pressure eutectic behavior. Melting rates are very slow and several hundred hours are required to establish equilibrium near the solidus. The subsolidus boundary for albite plus forsterite lies near that for sanidine plus forsterite, but with a shallower slope which more closely matches that of anorthite plus forsterite. Both albite plus forsterite and anorthite plus forsterite are replaced at high pressures by an assemblage containing clinopyroxene plus orthopyroxene, unlike sanidine plus forsterite, which is replaced by a feldspathoid plus orthopyroxene. The presence of sodium enlarges the depth region over which plagioclase lherzolite can stably exist; it may also stabilize alkali feldspar plus olivine in crustal rocks.     

»Late Jurassic« petroleum geology of the Dutch Central North Sea Graben

The Callovian to Ryazanian (late Middle Jurassic to earliest Cretaceous; here referred to as »Late Jurassic«) sediments of the Dutch Central North Sea Graben, comprising the Central Graben and Scruff Groups, form several potential reservoirs. Source rocks are present within both these groups and the Carboniferous and Late Triassic-Early Jurassic.The structural development of the area is illustrated by a number of cross-sections. A structural subdivision has been made into platform, intermediate platform, outer graben, and inner graben. The complex history of rifting, wrench-faulting, halokinesis, and structural inversion strongly influenced the palaeogeography and ensuing sandstone developments. A few selected burial-history plots are presented as examples of the relationship between the structural subdivision and the hydrocarbon potential of the area.

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Zusammenfassung Die Sedimente des Callov bis zum Ryazan (oberer Mitteljura bis unterste Kreide, hier als »Oberjura« bezeichnet) des zentralen niederländischen Nordsee-Grabens, der den Zentralgraben und die Scruff-Gruppe umfaßt, stellen mehrere potentielle Erdölspeichergesteine dar. In jeder dieser beiden Gruppen sowie im Karbon und von der Obertrias bis zur Unterkreide existieren Speichergesteine.Die strukturelle Entwicklung des Gebietes wird anhand mehrere Profile veranschaulicht. Außerdem schien eine Untergliederuntg in Plattform, Zwischenplattform, äußerer sowie innerer Graben sinnvoll. Die komplexe Entwicklungsgeschichte, die durch Riftingphasen, Wrench-Tektonik, Halokinese und Strukturinversion bestimmt wurde, hat die Paläogeographie und die resultierende Sandsteinbildung intensiv beeinflußt. Eine Anzahl ausgewählter Darstellungen der Geschichte der Sedimentüberlagerung dienen als Beispiele für den Zusammenhang zwischen den strukturell bestimmten Untergruppen und dem Kohlenwasserstoffpotential des Untersuchungsgebietes.

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Résumé Dans le secteur néerlandais du Graben Central de la Mer du Nord, plusieurs réservoirs potentiels sont constitués par les sédiments calloviens à ryazaniens (ensemble allant du sommet du Jurassique moyen au Crétacé inférieur et désigné ici par «Late Jurassic»). Ces sédiments comprennent le groupe du Graben central et le groupe de Scruff. Des rochesmères existent dans chacun de ces deux groupes ainsi que dans le Carbonifère et dans la série Trias terminal-Eojurassique.La constitution structurale de cette région est illustrée par une série de coupes. On distingue, au point de vue structural: une plate-forme, une plate-forme intermédiaire, un graben externe et un graben interne. L'histoire géologique complexe, avec ses processus de rifting, de décrochement, d'halokinèse et d'inversion structurale, s'est répercutèe de manière significative sur la paléogéographie et, par voie de conséquence, sur l'extension des faciès arénacés. Quelques reconstitutions de l'histoire sédimentaire sont présentées à titre d'exemple de manière à illustrer la relation entre les unités structurales et le potentiel en hydrocarbure de la région.

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Observations of mine seismicity in the eastern Wasatch Plateau,Utah, U.S.A.: A possible case of implosional failure

In the summer of 1984, a three-dimensional, high-resolution microearthquake network was operated in the vicinity of two coal mines beneath Gentry Mountain in the eastern Wasatch Plateau, Utah. During a six-week period, approximately 3,000 seismic events were observed of which the majority were impulsive, higher frequency (>10 Hz), short duration (<2–3 sec) events probably associated with the caving of the roof from a longwall operation. In contrast, 234 of the largest located events appeared to occur predominantlybeneath the mines to a depth of 2 to 3 km consistent with previous studies. The magnitudes of these events ranged from less thanM _c 0 to 1.6. In addition to the unusual depths of these latter events, an anomalous aspect displayed by the events was an apparent dilatational focal mechanism suggesting a non-double-couple, possibly implosional source. Implosional events have been observed in other studies of mine seismicity; however, the generally inadequate instrumental coverage of the focal sphere has cast some doubt on the validity of such mechanisms. Previously suggested source mechanisms for such implosional events have included tensional failure through strata collapse, and a shear-implosional displacement mechanism. Shear failure must be involved in the failure process of the Gentry Mountain implosional events as evidenced by well-defined shear waves in the observed seismograms. Simultaneous monitoring in the East Mountain coal mining area to the south by the University of Utah revealed typical shear failure events mixed with implosional events. The observed double-couple, reverse focal mechanisms at East Mountain were similar to mechanisms determined in previous studies and a composite focal mechanism determined in this study for a sequence outside the mining areas. This suggested that the shear events within the mining areas are being influenced by the regional tectonic stress field. Thus in addition to the seismic events associated with caving of the roof from the longwall operation, there appear to be at least two other types of mining-induced seismic events occurring in the eastern Wasatch Plateau, both submine in origin: (1) events characterized by apparent non-double-couple possibly implosional focal mechanisms and well-defined shear waves; and (2) shear events, which are indistinguishable from tectonic earthquakes and may be considered mining triggered earthquakes. The small mining-induced stress changes that occur beyond a few hundred meters from the mine workings suggest both types of seismic events are occurring on critically stressed, pre-existing zones of weakness. Topography, overburden, method of mining, and mine configuration also appear to be significant factors influencing the occurrence of the implosional submine events.