Th sorption and export models in the water column: A review

Over the past few decades, the radioisotope pair of ²³⁸U / ²³⁴Th has been widely and increasingly used to describe particle dynamics and particle export fluxes in a variety of aquatic systems. The present paper is one of five review articles dedicated to ²³⁴Th. It is focused on the models associated with ²³⁴Th whereas the companion papers (same issue) are focused on present and future methodologies and techniques (Rutgers van der Loeff et al.), C / ²³⁴Th ratios (Buesseler et al.), ²³⁴Th speciation (Santschi et al.) and present and future applications of ²³⁴Th [Waples, J.T., Benitez-Nelson, C.R., Savoye, N., Rutgers van der Loeff, M., Baskaran, M., Gustafsson, Ö., this issue. An Introduction to the application and future use of ²³⁴Th in aquatic systems. Marine Chemistry, FATE special issue]. In this paper, we review current ²³⁴Th scavenging models and discuss the relative importance of the non-steady state and physical terms associated with the most commonly used model to estimate ²³⁴Th flux. Based on this discussion we recommend that for future work the use of models should be accompanied by a discussion of the effect that model and data uncertainty have on the model results. We also suggest that future field work incorporate repeat occupations of sample sites on time scales of 1–4 weeks in order to evaluate steady state versus non-steady state estimates of ²³⁴Th export, especially during high flux events (> ca. 800 dpm m^− 2 d^− 1). Finally, knowledge of the physical oceanography of the study area is essential, particularly in ocean margins and in areas of established upwelling (e.g., Equatorial Pacific). These suggestions will greatly enhance the application of ²³⁴Th as a tracer of particle dynamics and flux in more complicated regimes.     

Equilibrium constants of triethanolamine in major seawater salts

Acid–base equilibrium constants of triethanolamine (TEA) have been determined by potentiometric titrations with a glass electrode, at 25 °C. Ionic strength was kept constant with only one electrolyte (using one of these salts: NaCl, KCl, MgCl₂ or CaCl₂), with binary mixtures of MgCl₂ and CaCl₂, and finally, in a solution with a composition approximately similar to that of natural seawater without sulfate. Equilibrium constants have been expressed in function of ionic strength by means of Pitzer equations and interaction parameters proposed in this theory have been obtained. It has been found that acid–base behaviour of TEA depends greatly on the salt used: basicity of TEA is decreased by CaCl₂, while it is increased by the other electrolytes used in this work.     

Coping with disaster: Rehabilitating coastal livelihoods and communities

This paper examines lessons from past approaches to natural disasters, as well as early lessons from the post-2004 Asian tsunami rehabilitation, to draw out general principles for rehabilitating livelihoods in poor coastal communities. We contend that avoiding the mistakes of the past requires: (1) a framework for understanding the diversity of coastal people's livelihood strategies and the sources of their vulnerability, (2) a process for designing interventions that build on this understanding in order to strengthen and revitalize coastal communities, including a means of assessing and selecting the most promising livelihood options, and (3) a focus on the longer-term challenge of building future resilience and sustainability in the communities by addressing the root causes of vulnerability.     

A climatology of mesoscale model simulated low-level wind jets over Cook Inlet and Shelikof Strait, Alaska

Weather in the North Gulf of Alaska is characterized by a high frequency of deep synoptic-scale low-pressure systems, especially during the cold season. The strong pressure gradients of these storms interact with the extremely rugged terrain of the coastal mountains to produce a variety of channeled flows. These surface wind regimes are not well documented in the scientific community, due to the paucity of observations. Modeling of these phenomena in regions of complex terrain is of great interest to those working with hydrodynamic, wave, and pollutant transport models in coastal and shelf areas. Such models, when coupled with ocean and coastal-ecology counterparts, give a broad view of the role surface winds play in shaping local coastal marine ecosystem in this region. This paper presents a climatology of simulated low-level wind jets over the domain of Cook Inlet and Shelikof Strait along Alaska's south-central coast. Daily simulations using the RAMS model were conducted in a 36-h forecast mode for the cold-season period 10/1/03 to 3/31/04. Systematic analysis of the resulting simulated low-level wind field makes it possible to characterize these jets and gap flows in spatial and temporal detail. The comparison between the RAMS winds and the Synthetic Aperture Radar (SAR)-derived winds when available verifies the existence of these wind jets and the capability of the model to simulate these cases. Clearly, the results of a study in this region depend on the fidelity of the model at these scales (O[5 km]). The SAR comparisons attempt to help establish this. From the 6 months of simulations over Cook Inlet and Shelikof Strait, the low-level wind jets are classified into 10 different regimes by location and orientation. These regimes are categorized into four more general groups: cross-channel westerly, easterly, and up and down Inlet flows. The nature of a particular regime is largely a function of pressure gradient orientation and local topography. Jets in the same group have a similar occurrence distribution with time. Some form of jet occurred in the study region almost daily each month of the period, with December 2003 having the highest frequency of wind jets.     

A note on ocean surface drift with application to surface velocities measured with HF Radar

The ocean drift current consists of a (local) pure drift current generated by the interaction of wind and waves at the sea surface, to which the surface geostrophic current is added vectorially. We present (a) a similarity solution for the wave boundary layer (which has been validated through the prediction of the 10-m drag law), from which the component of pure drift current along the direction of the wind (and hence the speed factor) can be evaluated from the 10-m wind speed and the peak wave period, and (b) a similarity solution for the Ekman layers of the two fluids, which shows that under steady-state neutral conditions the pure drift current lies along the direction of the geostrophic wind, and has a magnitude 0.034 that of the geostrophic wind speed. The co-existence of these two similarity solutions indicates that the frictional properties of the coupled air-sea system are easily evaluated functions of the 10-m wind speed and the peak wave period, and also leads to a simple expression for the angle of deflection of the pure drift current to the 10 m wind. The analysis provides a dynamical model for global ocean drift on monthly and annual time scales for which the steady-state neutral model is a good approximation. In particular, the theoretical results appear to be able to successfully predict the mean surface drift measured by HF Radar, which at present is the best technique for studying the near surface velocity profile.     

Exponential leap-forward gradient scheme for determining the isothermal layer depth from profile data

Two distinct layers usually exist in the upper ocean. The first has a near-zero vertical gradient in temperature (or density) from the surface and is called the isothermal layer (or mixed layer). Beneath that is a layer with a strong vertical gradient in temperature (or density), called the thermocline (or pycnocline). The isothermal layer depth (ILD) or mixed layer depth (MLD) for the same profile varies depending on the method used to determine it. Also, whether they are subjective or objective, existing methods of determining the ILD do not estimate the thermocline (pycnocline) gradient. Here, we propose a new exponential leap-forward gradient (ELG) method of determining the ILD that retains the strengths of subjective (simplicity) and objective (gradient change) methods and avoids their weaknesses (subjective methods are threshold-sensitive and objective methods are computationally intensive). This new method involves two steps: (1) the estimation of the thermocline gradient G _th for an individual temperature profile, and (2) the computation of the vertical gradient by averaging over gradients using exponential leap-forward steps. Such averaging can filter out noise in the profile data. Five existing methods of determining the ILD (difference, gradient, maximum curvature, maximum angle, and optimal linear fitting methods) as well as the proposed ELG method were verified using global expendable bathythermograph (XBT) temperature and conductivity–temperature–depth (CTD) datasets. Among all the methods considered, the ELG method yielded the highest skill score and the lowest Shannon information entropy (i.e., the lowest uncertainty).     

Morphology of Shatsky Rise oceanic plateau from high resolution bathymetry

Newly collected, high resolution multi-beam sonar data are combined with previous bathymetry data to produce an improved bathymetric map of Shatsky Rise oceanic plateau. Bathymetry data show that two massifs within Shatsky Rise are immense central volcanoes with gentle flank slopes declining from a central summit. Tamu Massif is a slightly elongated, dome-like volcanic edifice; Ori Massif is square shaped and smaller in area. Several down-to-basin normal faults are observed on the western flank of the massifs but they do not parallel the magnetic lineations, indicating that these faults are probably not related to spreading ridge faulting. Moreover, the faults are observed only on one side of the massifs, which is contrary to expectations from a mechanism of differential subsidence around the massif center. Multi-beam data show many small secondary cones with different shapes and sizes that are widely-distributed on Shatsky Rise massifs, which imply small late-stage magma sources scattered across the surface of the volcanoes in the form of lava flows or explosive volcanism. Erosional channels occur on the flanks of Shatsky Rise volcanoes due to mass wasting and display evidence of down-slope sediment movement. These channels are likely formed by sediments spalling off the edges of summit sediment cap.     

Characterisation and preliminary quantification of the methane reservoir in a coastal sedimentary source: San Simón Bay,Ría de Vigo,NW Spain

Ría de Vigo is a river valley flooded by the sea, with a bay (San Simón Bay) at its innermost part. The accumulation of Holocene sediment in San Simón Bay has been studied by the integration of 1) large scale high resolution seismic data, and 2) detailed geochemical analysis of a gravity core. In San Simón Bay the majority of the seismic records are obscured by acoustic turbidity which represents gassy sediments, but on records from Rande Strait it is possible to distinguish two Quaternary seismic sequences; an Upper Pleistocene sequence (SQ1) and a Holocene sequence (SQ2). Only SQ2 is recognized in San Simón Bay where it is comprised of two seismic units; the upper unit represents the HST sediment, i.e. the period of highest sea level. A gravity core taken within the gassy zone at 10 m water depth provided 3.55 m of fine-grained sediments (muds) from the youngest seismic unit (4 m thick). Geochemical analysis show high values (4 to 10%) of TOC. Sediment and porewater analyses indicate a distinct sulphate–methane transition zone (SMTZ) between 60 and 80 cm where sulphate is depleted (to <1.7 mM) and methane increases (to >0.4 mM). The top of the acoustic turbidity (the gas front) at 80 cm corresponds to the lower limit of the SMTZ. The methane cannot have been derived from the underlying metamorphic and granitic rocks, but was probably derived by microbial degradation of the organic matter in the Holocene sediments. We estimate that the sediments of the Bay contain approximately 1.8 × 10⁶ m³ of organic carbon and 275 ton of methane.     

The influence of island generated eddies on the carbon dioxide system, south of the Canary Islands

Measurements of surface partial pressure of CO₂ and water column alkalinity, pH_T, nutrients, oxygen, fluorescence and hydrography were carried out, south of the Canary Islands during September 1998. Cyclonic and anticyclonic eddies were alternatively observed from the northwestern area to the central area of the Canary Islands. Nutrient pumping and vertical uplifting of the deep chlorophyll maximum by cyclonic eddies were also ascertained by upward displacement of dissolved inorganic carbon. A model was applied to determine the net inorganic carbon balance in the cyclonic eddy. The fluxes were determined considering both the diffusive and convective contributions from the upward pumping and the corresponding horizontal transport of water outside the area. An increase in the total inorganic carbon concentration in the upper layers inside the eddy field of 133 mmol C m^− 2 d^− 1 was determined. The upward flux of inorganic carbon decreased the effect of the increased primary production on the carbon dioxide chemistry. The reduced fCO₂ inside the cyclonic eddy, 15 μatm lower than that observed in non-affected surface water, was explained by thermodynamic aspects, biological activity, eddy upward pumping and diffusion and air–sea water exchange effects.     

Chromium(VI) reduction by sulphur(IV) in aqueous solutions

The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔH_app of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression

−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]²