Optimisation of the Operation of an Electrochemical Process To Treat TBT‐contaminated Sediments on a Pilot Scale

Since at least three decades tributyltin had been commonly used in paint formulations to protect ship hulls and submersed surfaces from fouling. This has resulted in negative and Technology, effects to the marine environment due to its high toxicity towards non‐target organisms and to its accumulation in sediments, especially near point sources of pollution. Even if a ban of TBT for its application in anti‐fouling paints is enforced the problem of TBT‐contaminated sediments will remain for the coming years due to the low degradation rates of organotin in sediments. In this work an electrochemical process at a pilot scale to destroy TBT in sediments was investigated. Previous experiences at a laboratory and technical scale have demonstrated the potential of this process to electrolytically degrade organotin species in sediments. This article deals with the optimisation of the pilot plant performance in terms of organotin degradation and operation costs monitoring additionally the effect of the electrochemical treatment on other pollutants such as heavy metals, PCBs, and PAHs. The aim was to investigate by means of a parametric study the range of operating conditions required to destroy TBT down to concentrations lower than 100 μg/kg; to determine the influence of those parameters on the performance of the process; and to evaluate the operation costs associated to the process. It was determined that it was possible to destroy TBT down to 100 μg/kg at current densities in the range of 4.4 to 6.6 mA/cm² and chloride concentrations of least of 0.2 mol/L with operation costs of 13 to 18 EUR/m³.     

Slow drift oscillations of a ship in irregular waves

A procedure to calculate horizontal slow drift excitation forces on an infinitely long horizontal cylinder in irregular beam sea waves is presented. The hydrodynamic boundary-value problem is solved correctly to second order in wave amplitude. Results in the form of second order transfer functions are presented for different two-dimensional shapes. It is concluded that Newman's approximative method is a practical way to calculate slow drift excitation forces on a ship in beam sea and suggested that it may be used in a more general case. Applications of the results for moored ships are discussed.     

Assessing the Validity of Seismo-Acoustic Predictor Equations for Obtaining Seabed and Sub-Surface Sediment Physical Properties

The interdependence between the seismo-acoustic properties of a marine sediment and its geotechnical/physical parameters has been known for many years, and it has been postulated that this should allow the extraction of geotechnical information from seismic data. Though in the literature many correlations have been published for the surficial layer, there is a lack of information for greater sediment depths. In this article, a desktop study on a synthetic seafloor model illustrates how the application of published near-surface prediction equations to subsurface sediments (up to several tens of meters burial depth) can lead to spurious predictions. To test this further, acoustic and geotechnical properties were measured on a number of sediment core samples, some of which were subjected to loading in acoustically-equipped consolidation cells (oedometers) to simulate greater burial depth conditions. For low effective pressures (representing small burial depths extending to around 10 meters subsurface), the general applicability of established relationships was confirmed: the prediction of porosity, bulk density, and mean grain size from acoustic velocity and impedance appears generally possible for the investigated sedimentary environments. As effective pressure increases through, the observed relationships deviate more and more from the established ones for the near-surface area. For the samples tested in this study, in some instances increasing pressure even resulted in decreasing velocities. There are several possible explanations for this abnormal behavior, including the presence of gas, overconsolidation, or bimodal grain size distribution. The results indicate that an appropriate depth correction must be introduced into the published prediction equations in order to obtain reliable estimates of physical sediment properties for greater subsurface depths.     

The carbon dioxide system in the northwestern Indian Ocean during south–west monsoon

Data on the carbonate system of the Northwestern Indian Ocean obtained on a cruise of F.S. Meteor during SW monsoon in July/August 1995 were compared with those of George et al. [George, M.D., Kumar, M.D., Naqvi, S.W.A., Banerjee, S., Narvekar, P.V., de Sousa, S.N., Jayakumar, D.A., 1994. A study of the carbon dioxide system in the northern Indian Ocean during premonsoon. Mar. Chem. 47, 243–254] collected during intermonsoon. In general, deep water values agreed well between the two expeditions. Surface waters, however, showed a substantial increase in dissolved inorganic carbon (C_T) in the coastal regions due to strong upwelling in the SW monsoon. This was also accompanied by very high CO₂ partial pressures in surface waters. The north–south gradients in vertical profiles of the measured parameters in the Arabian Sea are discussed by comparing profiles from the oligotrophic equatorial region with those from the highly productive central Arabian Sea. The effect of denitrification on regenerated C_T and A_T is minor, with contributions of <9 and <8 μmol kg⁻¹, respectively, to the total amount regenerated also utilizing oxygen. The dissolution of biogenic carbonates is discussed; different approaches to define the depth, where the dissolution starts (lysocline(s), carbonate critical depth (CCrD)), are compared together with the calculation of saturation depth from carbonate concentrations. It is shown, that small differences in measured C_T and A_T (found between our data and those measured during GEOSECS) and different calculation approaches to the CO₂ system (different dissociation constants for species involved and taking into account phosphate and silicate concentrations) can produce pronounced differences in the calculated saturation depths. However, C_T and A_T data suggest substantial dissolution of biogenic carbonate in the water column even above the calcite lysocline, irrespective of the procedures followed to calculate this horizon.     

Dehydration of clastic sediments in subduction zones: Theoretical study using thermodynamic data of minerals

Pseudosections for two sediments and one basalt calculated in the system K₂O–Na₂O–CaO–MgO–FeO–Fe₂O₃–Al₂O₃–TiO₂–SiO₂–H₂O for the P–T range 10 to 35 kbar, 300 to 900°C give useful insights into the amount of H₂O released from oceanic crust in subduction zones. In cold subduction zones (20 kbar–300°C to 35 kbar–500°C) hydrous minerals storing 3 to 4 wt% H₂O are still present in metasediments at depths of 120 km. In the same environment, metabasite releases 1 wt% H₂O in the depth range 100 to 120 km, but 4.5 wt% H₂O is transported to greater depths. In hot subduction zones (300°C hotter than the cold subduction zone at 100 km depth), dehydration events of metasediments in the depth range 50 to 80 km correspond to the breakdown of chlorite and paragonite. In the calculations no further water is released at greater depths because the modal content of phengite, the only hydrous mineral phase at these depths, remains almost constant. For the same P–T path, metabasite shows continuous dehydration between 40 and 80 km releasing almost 3 wt% H₂O. At 120 km depth less than 0.4 wt% of H₂O remains. In an average modern subduction zone (～6°C/km) most dehydration of sediments occurs at depths of 70 to 100 km and that of basalts at depths of 80 to 120 km. Only 1.3 wt% H₂O in metasediments and 1.6 wt% H₂O in metabasalt has the potential to be subducted to depths greater than 120 km. The dehydration behavior of sediments concurs with the generally held idea that subduction zone fluids are most effectively transported to great depths by cold subduction. In hot subduction zones, such as those characteristic of early Earth, most H₂O carried by oceanic crust is liberated at depths less than 120 km and, thus, would not contribute to island‐arc magmatism.     

The international at-sea intercomparison of fCO2 systems during the R/V Meteor Cruise 36/1 in the North Atlantic Ocean

The ‘International Intercomparison Exercise of fCO₂ Systems’ was carried out in 1996 during the R/V Meteor Cruise 36/1 from Bermuda/UK to Gran Canaria/Spain. Nine groups from six countries (Australia, Denmark, France, Germany, Japan, USA) participated in this exercise, bringing together 15 participants with seven underway fugacity of carbon dioxide (fCO₂) systems, one discrete fCO₂ system, and two underway pH systems, as well as systems for discrete measurement of total alkalinity and total dissolved inorganic carbon. Here, we compare surface seawater fCO₂ measured synchronously by all participating instruments. A common infrastructure (seawater and calibration gas supply), different quality checks (performance of calibration procedures for CO₂, temperature measurements) and a common procedure for calculation of final fCO₂ were provided to reduce the largest possible amount of controllable sources of error. The results show that under such conditions underway measurements of the fCO₂ in surface seawater and overlying air can be made to a high degree of agreement (±1 μatm) with a variety of possible equilibrator and system designs. Also, discrete fCO₂ measurements can be made in good agreement (±3 μatm) with underway fCO₂ data sets. However, even well-designed systems, which are operated without any obvious sign of malfunction, can show significant differences of the order of 10 μatm. Based on our results, no “best choice” for the type of the equilibrator nor specifics on its dimensions and flow rates of seawater and air can be made in regard to the achievable accuracy of the fCO₂ system. Measurements of equilibrator temperature do not seem to be made with the required accuracy resulting in significant errors in fCO₂ results. Calculation of fCO₂ from high-quality total dissolved inorganic carbon (C_T) and total alkalinity (A_T) measurements does not yield results comparable in accuracy and precision to fCO₂ measurements.     

Coordinated Ocean-ice Reference Experiments (COREs)

Coordinated Ocean-ice Reference Experiments (COREs) are presented as a tool to explore the behaviour of global ocean-ice models under forcing from a common atmospheric dataset. We highlight issues arising when designing coupled global ocean and sea ice experiments, such as difficulties formulating a consistent forcing methodology and experimental protocol. Particular focus is given to the hydrological forcing, the details of which are key to realizing simulations with stable meridional overturning circulations.The atmospheric forcing from [Large, W., Yeager, S., 2004. Diurnal to decadal global forcing for ocean and sea-ice models: the data sets and flux climatologies. NCAR Technical Note: NCAR/TN-460+STR. CGD Division of the National Center for Atmospheric Research] was developed for coupled-ocean and sea ice models. We found it to be suitable for our purposes, even though its evaluation originally focussed more on the ocean than on the sea-ice. Simulations with this atmospheric forcing are presented from seven global ocean-ice models using the CORE-I design (repeating annual cycle of atmospheric forcing for 500 years). These simulations test the hypothesis that global ocean-ice models run under the same atmospheric state produce qualitatively similar simulations. The validity of this hypothesis is shown to depend on the chosen diagnostic. The CORE simulations provide feedback to the fidelity of the atmospheric forcing and model configuration, with identification of biases promoting avenues for forcing dataset and/or model development.     

A Bayesian hierarchical spatio-temporal model for significant wave height in the North Atlantic

Bad weather and rough seas continue to be a major cause for ship losses and is thus a significant contributor to the risk to maritime transportation. This stresses the importance of taking severe sea state conditions adequately into account in ship design and operation. Hence, there is a need for appropriate stochastic models describing the variability of sea states, taking into account long-term trends related to climate change. Various stochastic models of significant wave height are reported in the literature, but most are based on point measurements without considering spatial variations. As far as the authors are aware, no model of significant wave height to date exploits the flexible framework of Bayesian hierarchical space-time models. This framework allows modelling of complex dependence structures in space and time and incorporation of physical features and prior knowledge, yet at the same time remains intuitive and easily interpreted. This paper presents a Bayesian hierarchical space-time model for significant wave height. The model has been fitted by significant wave height data for an area in the North Atlantic ocean. The different components of the model will be outlined, and the results from applying the model to monthly and daily data will be discussed. Different model alternatives have been tried and long-term trends in the data have been identified for all model alternatives. Overall, these trends are in reasonable agreement and also agree fairly well with previous studies. Furthermore, a discussion of possible extensions to the model, e.g. incorporating regression terms with relevant meteorological data will be presented.     

Semantic Enablement for Spatial Data Infrastructures

Building on abstract reference models, the Open Geospatial Consortium (OGC) has established standards for storing, discovering, and processing geographical information. These standards act as a basis for the implementation of specific services and Spatial Data Infrastructures (SDI). Research on geo‐semantics plays an increasing role to support complex queries and retrieval across heterogeneous information sources, as well as for service orchestration, semantic translation, and on‐the‐fly integration. So far, this research targets individual solutions or focuses on the Semantic Web, leaving the integration into SDI aside. What is missing is a shared and transparent Semantic Enablement Layer for SDI which also integrates reasoning services known from the Semantic Web. Instead of developing new semantically enabled services from scratch, we propose to create profiles of existing services that implement a transparent mapping between the OGC and the Semantic Web world. Finally, we point out how to combine SDI with linked data.