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.     

Pathways of clay mineral transport in the coastal zone of the Brazilian continental shelf from Ceará to the mouth of the Amazon River

The transport pathways of fine sediments (fraction <2 μm) along the Brazilian continental shelf from Ceará to the Amazon River mouth were studied by means of clay mineral analyses. On the continental shelf southeast of the Amazon mouth, fluctuations in clay mineral compositions reflect simple mixing between the suspended load of the North Brazil Current and sediment from several smaller rivers. Previously, clay mineral variations west of the Amazon mouth have been explained by variable settling velocities of different grain-size classes within the <2 μm fraction or by selective coagulation of individual clay mineral groups. By contrast, our experiments with river bank samples show that selective coagulation does not occur in Amazon River sediments. A more appropriate explanation for observed variations in clay mineral composition off the Amazon mouth seems to be, similarly to that for the shelf between Ceará and the Amazon mouth, a mixing of Amazon sediments with suspended material of the North Brazil Current. This interpretation is supported by data on clay mineral composition east and south of the Amazon mouth, showing more affinity to sediments of the North Brazil Current than to the suspended load of the Amazon River. Additionally, relatively low sedimentation rates and low concentrations of fine-grained sediments on the shelf suggest that high riverine input by the Amazon River does not overprint the sediments of the North Brazil Current in this region. The strong North Brazil Current shunts the Amazon suspended load in a north-westerly direction along the north-eastern coast of South America. Hence, stronger sedimentation of Amazon sediments would occur only west of the river mouth.     

Nutrient budgets and trophic state in a hypersaline coastal lagoon: Lagoa de Araruama, Brazil

Lagoa de Araruama in the state of Rio de Janeiro, Brazil, is a hypersaline lagoon with salinity varying spatially from 45 to 56. We collected water samples during monthly cruises throughout the lagoon, and along the streams feeding the system, from April 1991 to March 1992. Nutrients and other water quality parameters exhibited great spatial and temporal variations. Mass balance calculations indicate large amounts of anthropogenic nutrient inputs. The data indicate that the lagoon currently is oligotrophic but is in a state of transition to become a mesotrophic system. Molar dissolved inorganic nitrogen:dissolved inorganic phosphorus (DIN/DIP) varied between 2.2:1 and 659:1 with a volume-weighted average of 22:1. The high DIN/DIP ratio contrasts with that found in nearby lagoons, suggesting that phytoplankton primary production is limited by phosphorus in Lagoa de Araruama. The major loss of DIP is apparently driven by biological assimilation and diagenic reactions in the sediments. Calculations indicate that the lagoon is slightly net autotrophic at +0.9 mol C m⁻² yr⁻¹. This suggests that the biomass of the primary producers is restricted by phosphorus availability. Phosphorus retention in the sediment and the hypersaline state of the lagoon prevent changes in autotrophic communities and the formation of eutrophic conditions.     

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.     

The Bayesian detection of discontinuities in a polynomial regression and its application to the cycle-slip problem

This paper deals with the problem of detecting and correcting cycle-slips in Global Navigation Satellite System (GNSS) phase data by exploiting the Bayesian theory. The method is here applied to undifferenced observations, because repairing cycle-slips already at this stage could be a useful pre-processing tool, especially for a network of permanent GNSS stations. If a dual frequency receiver is available, the cycle-slips can be easily detected by combining two phase observations or phase and range observations from a single satellite to a single receiver. These combinations, expressed in a distance unit form, are completely free from the geometry and depend only on the ionospheric effect, on the electronic biases and on the initial integer ambiguities; since these terms are expected to be smooth in time, at least in a short period, a cycle-slip in one or both the two carriers can be modelled as a discontinuity in a polynomial regression. The proposed method consists in applying the Bayesian theory to compute the marginal posterior distribution of the discontinuity epoch and to detect it as a maximum a posteriori (MAP) in a very accurate way. Concerning the cycle-slip correction, a couple of simultaneous integer slips in the two carriers is chosen by maximazing the conditional posterior distribution of the discontinuity amplitude given the detected epoch. Numerical experiments on simulated and real data show that the discontinuities with an amplitude 2 or 3 times larger than the noise standard deviation are successfully identified. This means that the Bayesian approach is able to detect and correct cycle-slips using undifferenced GNSS observations even if the slip occurs by one cycle. A comparison with the scientific software BERNESE 5.0 confirms the good performance of the proposed method, especially when data sampled at high frequency (e.g. every 1 s or every 5 s) are available.     

Modelling Positional Uncertainty of Line Features by Accounting for Stochastic Deviations from Straight Line Segments

The assessment of positional uncertainty in line and area features is often based on uncertainty in the coordinates of their elementary vertices which are assumed to be connected by straight lines. Such an approach disregards uncertainty caused by sampling and approximation of a curvilinear feature by a sequence of straight line segments. In this article, a method is proposed that also allows for the latter type of uncertainty by modelling random rectangular deviations from the conventional straight line segments. Using the model on a dense network of sub‐vertices, the contribution of uncertainty due to approximation is emphasised; the sampling effect can be assessed by applying it on a small set of randomly inserted sub‐vertices. A case study demonstrates a feasible way of parameterisation based on assumptions of joint normal distributions for positional errors of the vertices and the rectangular deviations and a uniform distribution of missed sub‐vertices along line segments. Depending on the magnitudes of the different sources of uncertainty, not accounting for potential deviations from straight line segments may drastically underestimate the positional uncertainty of line features.