Computing Lippmann Diagrams from Direct Calculation of Mixing Properties of Solid Solutions: Application to the Barite-Celestite System

The Lippmann diagram for the system(Ba, Sr)SO₄-H₂O was computed at 25 °Cby determining the solid-phase activity coefficientsfrom first principles calculations. Directcalculations of the mixing properties of thebarite-celestite series indicate this solid solutionbehaves as non-ideal and non-regular. At 25 °C,the enthalpy of mixing shows a minimum around 50 mole% SrSO₄ due to an ordering tendency. Thefree energy of mixing shows two minima that delimit awide and symmetric miscibility gap (from 2.1 to 97.9 mole% SrSO₄) at this temperature. The excessfree energy of mixing requires a Guggenheim expansionseries of 5 terms to be described, where the termswith odd exponents are null as a consequence of thesymmetric distribution of the mixing properties withcomposition. The Lippmann diagram shows a peritecticpoint that corresponds to the composition of an aqueoussolution which is simultaneously at equilibrium withthe two extremes of the miscibility gap. The largedifference between the solubility products of theendmembers involves a strong preferential partitioningof the less soluble endmember towards the solid phase,which explains the extremely Ba-poor composition ofthe aqueous solution (aqueous activity fraction forBa²⁺ = 0.000446 ) at the peritectic point.     

A note on climate change adaptation for seaports: a challenge for global ports, a challenge for global society

With 80 % of world trade carried by sea, seaports provide crucial linkages in global supply-chains and are essential for the ability of all countries to access global markets. Seaports are likely to be affected directly and indirectly by climatic changes, with broader implications for international trade and development. Due to their coastal location, seaports are particularly vulnerable to extreme weather events associated with increasing sea levels and tropical storm activity, as illustrated by hurricane “Sandy”. In view of their strategic role as part of the globalized trading system, adapting ports in different parts of the world to the impacts of climate change is of considerable importance. Reflecting the views of a diverse group of stakeholders with expertise in climate science, engineering, economics, policy, and port management, this essay highlights the climate change challenge for ports and suggests a way forward through the adoption of some initial measures. These include both “soft” and “hard” adaptations that may be spearheaded by individual port entities, but will require collaboration and support from a broad range of public and private sector stakeholders and from society at large. In particular, the essay highlights a need to shift to more holistic planning, investment and operation.     

Analyses of pre-injection reservoir data for stable carbon isotope trend predictions in CO2 monitoring: preparing for CO2 injection

Baseline monitoring at the proposed enhanced gas recovery site in Altmark (Germany) was carried out in combination with theoretical and laboratory investigations to describe and predict the principles of expected stable carbon isotope and dissolved inorganic carbon (DIC) trends during CO₂ injection in reservoirs. This provides fundamental data for site-specific characterisation for monitoring purposes. Baseline ??¹³C values at the Altmark site ranged between ?1.8 and ?11.5??? and DIC values were about 2?mmol?L^?1. These baseline values form the basis for a theoretical study on the influences of the ambient reservoir conditions on the state of geochemical and isotope equilibrium of the reservoir fluids. Transferring this theoretical study to the Altmark site enables predictions on geochemical trends during potential injection. Assuming that CO₂ would be injected at the Altmark site to pCO₂?=?100?bar and with a ??¹³C of ?30???, at isotopic and geochemical equilibrium, ??¹³C_DIC values would approach this end-member, and DIC concentrations of 1,000?mmol L^?1 would be expected. Laboratory experiments were conducted at low pCO₂ levels (4?C35?bars) to mimic the approach of a CO₂ plume at a monitoring well. These results support field investigations from other sites: that ??¹³C_DIC is a sensitive tool for monitoring CO₂ migration in the subsurface and simultaneously allows quantification of geochemical trapping of CO₂.     

Emplacement of the Ardara pluton (Ireland): new constraints from magnetic fabrics, rock fabrics and age dating

The Ardara pluton as part of the Donegal batholith was intruded into Neoproterozoic metasediments and metadolerites at mid-crustal levels. The emplacement mechanism of the Ardara granite is very controversial, and mechanisms ranging from diapirism, ballooning and stoping followed by nested diapirism have been proposed. Magnetic fabrics, rock fabrics and K/Ar dating of micas are used here to constrain the emplacement history. The compositional zoning of the Ardara pluton is clearly reflected in the different bulk magnetic susceptibilities between the outer quartz monzodiorite and the central granodiorite, whereas the intervening tonalite is of intermediate nature. The magnetic carriers are characterized by the anisotropy of the magnetic susceptibility (AMS), thermomagnetic measurements and through high field analyses (HFA). The separation of the ferrimagnetic and paramagnetic contributions revealed that biotite and magnetite control the AMS in the quartz monzodiorite. Both minerals are oriented in such a way that their summed contribution is constructive and originates from the shape fabric of magnetite and the texture of biotite. Biotite is responsible mainly for the AMS in the tonalite and granodiorite. The magnetic foliation can be directly related to the macroscopic foliation and also to the D4 structures in the country rocks. The foliation is consistent with the geometry of the roughly circular shape and has a mostly steep to vertical dip. Towards the central granodiorite the magnetic foliation dies out, although plagioclase texture measurements indicate a weak magmatic shape fabric. With the exception of the tail, the K_max axes (magnetic lineation) vary from steeply to gently plunging. The so-called lineation factor is approximately 1.01 and therefore points to a less significant axial symmetry. These observations coincide with strain estimates on mafic enclaves that show a very consistent pattern of K ∼0 flattening strain. Texture analyses of biotite and quartz additionally support the observations made by the strain analyses and the magnetic fabric data. Microstructural investigations give evidence that the fabrics are associated with the emplacement over a range of temperatures from truly magmatic to high-temperature solid-state conditions. The age of the intrusion is still under discussion, but a new cooling age was determined by K/Ar dating of biotite at 403.7±8 Ma corresponding to a temperature range between 450 and 300°C. For a mylonite along the southern contact between the Ardara pluton and the country rock a K/Ar muscovite age of 378.8±7 Ma indicates a minimum age for the shear zone when the Ardara pluton must have already been cooled down below 350±50°C. Received: 28 January 1999 / Accepted: 28 December 1999     

Carbon,hydrogen and nitrogen isotopes in solvent-extractable organic matter from carbonaceous chondrites

Solvent extractions were done on the carbonaceous chondrites Murray, Murchison, Orgueil and Renazzo, using CCl₄ and CH₃OH. Between 2 and 10% of the total carbon in these meteorites is extractable by ordinary techniques, most of it in CH₃OH. After demineralization with HF, perhaps as much as 30% of the total carbon in Murray may be extractable with CH₃OH. The extracts from Renazzo have isotopic ratios which suggest that they are mainly terrestrial organic matter, with lesser contributions from indigenous organics. The CH₃OH-soluble organic matter from Murchison and both untreated and HF-treated Murray has δ¹³C values of about +5 to + 10%. and δ¹⁵N values of about +90 to +100%., both of which are significantly higher than the bulk meteorite values. The Orgueil CH₃OH-extract also has a δ¹⁵N value well above the value in residual organic matter. Values for δD of +300 to +500%. are found for the CH₃OH-soluble organic matter. The combined data for C, H and N isotopes makes it highly unlikely that the CH₃OH-soluble components are derivable from, or simply related to, the insoluble organic polymer found in the same meteorites. A relationship is suggested between the event that formed hydrous minerals in CI1 and CM2 meteorites and the introduction of water-soluble (methanol-soluble) organic compounds. Organic matter soluble in CCl₄ has essentially no nitrogen, and δ³C and δD values are lower than for CH₃OH-soluble phases. Either there are large isotopic fractionations for carbon and hydrogen between different soluble organic phases, or the less polar components are partially of terrestrial origin.     

Interpolation using a generalized Green's function for a spherical surface spline in tension

A variety of methods exist for interpolating Cartesian or spherical surface data onto an equidistant lattice in a procedure known as gridding. Methods based on Green's functions are particularly simple to implement. In such methods, the Green's function for the gridding operator is determined and the resulting gridding solution is composed of the superposition of contributions from each data constraint, weighted by the Green's function evaluated for all output–input point separations. The Green's function method allows for considerable flexibility, such as complete freedom in specifying where the solution will be evaluated (it does not have to be on a lattice) and the ability to include both surface heights and surface gradients as data constraints. Green's function solutions for Cartesian data in 1-, 2- and 3-D spaces are well known, as is the dilogarithm solution for minimum curvature spline on a spherical surface. Here, the spherical surface case is extended to include tension and the new generalized Green's function is derived. It is shown that the new function reduces to the dilogarithm solution in the limit of zero tension. Properties of the new function are examined and the new gridding method is implemented in Matlab® and demonstrated on three geophysical data sets.     

Contaminant concentrations in sport fish from San Francisco Bay, 1997

In 1997, seven sport fish species were sampled from seven popular fishing areas in San Francisco Bay. Mercury exceeded a human health screening value in 44 of 84 (52%) samples. All collected samples of leopard shark and striped bass exceeded the mercury screening value of 0.23 microg/g wet weight. PCBs exceeded the screening value in 51 of 72 (71%) samples. DDT, chlordane, and dieldrin, had lower numbers of samples above screening values: 16 of 72 (22%) for DDT, 11 of 72 (15%) for chlordanes, and 27 of 72 (37%) for dieldrin. Concentrations of PCBs and other trace organics were highest in white croaker and shiner surfperch, the two species with the highest fat content in their muscle tissue. Fish from one location, Oakland Harbor, had significantly elevated wet weight concentrations of mercury, PCBs, DDTs, and chlordanes compared to other locations. Removal of skin from white croaker fillets reduced lipid concentrations by 27-49% and concentrations of trace organics by 33-40%.