Lesser-known consequences of managing marine fisheries using individual transferable quotas

Managing marine fisheries using output controls in the form of individual transferable quotas (ITQs) can be an attractive alternative to more traditional input controls. There are now a number of examples of where ITQ-managed fisheries have been able to reduce the impact of the major management problems in global fisheries, namely, gross over-capitalisation and effort. However, ITQs are not the perfect management tool and one of the lesser known consequences of ITQ-managed fisheries where ITQs consist of a harvest right is the implicit relationship between ITQ property rights and rights of access to the fishing grounds. This implicit spatial right to the grounds can provide obstacles in the way of allocating water-space within fishing grounds for alternative uses such as marine-protected areas, large-scale aquaculture, and wind farms. These lesser-known consequences of ITQ-managed fisheries are discussed here.     

Uptake and transformation of C-labelled tributyltin chloride by the dog-whelk, nucella lapillus: Importance of absorption from the diet

The importance of the diet as a source of tributyltin (TBT) in Nucella lapillus was studied using [¹⁴C]tributyltin chloride. In N. lapillus provided with prelabelled mussels, Mytilus edulis, in labelled water (mean 20·5 ng/litre TBT) the rate of accumulation of total ¹⁴C was 2–3 times that in unfed animals. Owing to its degradation in the tissues of both fed and unfed animals, concentrations of [¹⁴C]TBT tended to reach a plateau after only 28 days. However, total concentrations of ¹⁴C were still increasing after 49 days. Under experimental conditions (15°C, ample food, no disturbance) the diet accounted for about 50% of the body burden of TBT in N. lapillus after 49 days exposure: concentration factors (dry tissue/water) for [¹⁴C]TBT in both male and female N. lapillus were similar at about 60 000 in fed and 30 000 in unfed animals. It is concluded that the diet may contribute less than half of the body burden of TBT found in natural populations subjected to life-long exposure.     

Identifying Source Soils in Contemporary Estuarine Sediments: A New Compound-Specific Isotope Method

A new method is proposed for the identification and apportionment of contemporary source soils contributing to estuarine sediments. The method uses compound-specific isotopic analysis of naturally occurring biomarkers (fatty acids) derived from plants to link source soils to land use within a single catchment. For identification and apportionment of source soils in the estuarine samples, the method uses the isotopic mixing model, IsoSource. The feasible proportions obtained from IsoSource are then scaled to allow for the percent organic carbon in the source soils. With this approach, the estimation of each source soil contribution to a location in the estuary is independent of any degradation of the biomarkers through microbial or biogeochemical processes. Identification relies on the evaluation of the sediment sample relative to a “library” of reference source soils from different land use within the catchment. Selection of potential sources is geographically constrained by the requirement for a natural linkage between each source soil and the sediment site sampled. A case study, using this method, mapped the distribution of three main land use source soils (pasture, native forest, and pine forest) across the river delta in a small estuary fringed with mangroves. Rather than being uniformly distributed, the results indicated that the source soil contributions varied markedly across the delta, raising concerns about the validity of taking single cores to characterize the sediments of an estuary. Coupling the source apportionment results with land use data indicated that the mean percent contribution of pine forest soil in the river delta sediments was almost three times greater than the percent land use area of pine forest in the catchment. Furthermore, isotopic signatures indicated that most of the pine forest soil came from the much smaller areas exposed to erosion by clear cut harvesting and that the soil contribution from recently harvested areas of pine forest could be as much as 20 times greater than that land use area in this catchment. This is the first method that can identify and apportion, by land use on a catchment scale, the sources of soil contributing to the sediment at a location of an estuary. The results are given as a “best estimate”, within definable limits, of the proportional contribution of each potential source soil. Information obtained using this method will allow development of management strategies to alter land use practices to reduce the sediment load to rivers, and thus, the impact on the aquatic ecosystem downstream in estuaries.     

Compression mechanisms of coesite

 The structure of coesite has been determined at ten pressures up to a maximum of 8.68 GPa by single-crystal X-ray diffraction. The dominant mechanism of compression is the reduction of four of the five independent Si–O–Si angles within the structure. There is no evidence of the fifth linkage, Si1–O1–Si1, deviating from 180°. Some Si–O bond distances also decrease by up to 1.6% over the pressure range studied. The pattern of Si–O–Si angle reduction amounts to a rotation of the Si2 tetrahedron around the [001] direction. This rotation induces significant internal deformation of the Si1 tetrahedron. Comparison of the experimental data with rigid-unit distance least-squares simulations of coesite suggests that this pattern of compression, the anomalous positive values of both s₂₃ and K′′ in the equation of state of coesite, its high elastic anisotropy and the unusual straight Si1–O1–Si1 linkage within the structure are all consequences of the connectivity of the tetrahedral framework. Received: 11 July 2002 / Accepted: 14 January 2003 Acknowledgements The help of Christian Baerlocher of ETH Zurich in providing both the DLS-76 software and advice in its use is gratefully acknowledged, as are discussions with Paul Ribbe of Virginia Tech and the comments of two anonymous reviewers. The data analysis was supported by the National Science Foundation under grant EAR-0105864 to N.L. Ross and R.J. Angel.     

The bottom sediments of the Amazon shelf and tropical Atlantic Ocean

Analytical results of bottom sampling of the equatorial Atlantic Ocean affected by the Amazon River show a concentration of material smaller than 2 μ along the shore northwest of the mouth of the Amazon River for 2000 km. A zone having a high percentage of material coarser than 20 μ extends outward from the Amazon River and along the outer continental shelf northwestward for 2000 km. Areas having high carbonate percentages are encountered only on the outer shelf and in deep water.     

Quantum mechanical potential surfaces and calculations on minerals and molecular clusters

Recently, ab-initio quantum mechanical potential surfaces calculated for silicate hydroxyacid molecules were used to extract covalent potentials for use in mineral physics calculations (Lasaga and Gibbs 1987). The calculations showed that these potentials are capable of generating the structure and physical properties of silicate minerals. In this paper we explore in more detail the suitability of various covalent potentials in mimicking the topography of the ab-initio potential surfaces. We also extend the use of such quantum-derived potentials in generating the structures of hydroxyacid dimers, trimers, and pentamers of silicate tetrahedra and in studying the structure and the dynamical properties of minerals and glasses.     

A modeling of the structure and compressibility of quartz with a molecular potential and its transferability to cristobalite and coesite

Several computer models of quartz were developed and tested. A simple model based on a potential energy function, derived in large part from quantum mechanical calculations on the molecule H₆Si₂O₇, was found to reproduce the compressibility curve for quartz up to pressures of 8 GPa. The potential includes quadratic expressions for the SiO bond lengths, the OSiO angles and a parameter spanning the SiOSi angle together with an exponential OO repulsion term for non co-dimer O atoms. The variations in the cell edges and in the SiOSi angle, as a function of pressure, parallel observed trends when the bond lengths and angles calculated for the molecule are used as rgressor values. Poisson ratios calculated using the model match those observed. Two configurations for quartz related by the Dauphiné twin law are generated as minimum energy structures of the model with about equal frequencies as observed in nature. It is shown that the model, devised for quartz, can also be applied to the silica polymorph cristobalite, giving reasonable estimates of its compressibility curve, structural parameters and its negative Poisson ratio. When the observed bond lengths and angles are used as regressor values, the model generates the absolute coordinates of the atoms and the cell dimensions for quartz to within 0.005 Å and those of cristobalite to within 0.001 Å, on average, both at zero pressure. When applied to coesite, the model yields a zero pressure structure that is close to that observed but which is significantly softer than observed. The resulting SiO bond lengths are linearly correlated with f _s (O), as observed for coesite, despite the use of a single bond length and a single SiOSi angle as regressor values in the calculation. When the structures are optimized assuming P1 space group symmetry and triclinic cell dimensions, the resulting frameworks of silicate tetrahedra exhibit the translational, rotational and reflection symmetries observed for quartz, cristobalite and coesite. The fact that the resulting frameworks exhibit observed space group symmetries is evidence that the symmetry adopted by the silica polymorphs can be explained by short ranged forces.     

Bond length and radii variations in fluoride and oxide molecules and crystals

Molecular orbital calculations completed on fluoride molecules containing first and second row cations have generated bond lengths, R, that match those observed for coordinated polyhedra in crystals to within ～0.04 Å, on average. The calculated bond lengths and those observed for fluoride crystals can be ranked with the expression R=Kp ^?0.22, where p=s/r, s is the Pauling strength of the bond, r is the row number of the cation and K=1.34. The exponent -0.22 (≈ -2/9) is the same as that observed for oxide, nitride and sulfide molecules and crystals. Bonded radii for the fluoride anion, obtained from theoretical electron density maps, increase linearly with bond length. Those calculated for the cations as well as for the fluoride anion match calculated promolecule radii to within ～0.03 Å, on average, suggesting that the electron density distributions in the vicinity of the minima along the bond paths possess a significant atomic component despite bond type. Bonded radii for Si and O ions provided by experimental electron density maps measured for the oxides coesite, danburite and stishovite match those calculated for a series of monosilicic acid molecules. The resulting radii increase with bond length and coordination number with the radius of the oxide ion increasing at a faster rate than that of the Si cation. The oxide ion within danburite exhibits several distinct radii, ranging between 0.9 and 1.2 Å, rather than a single radius with each exhibiting a different radius along each of the nonequivalent bonds with B, Si and Ca. Promolecule radii calculated for the coordinated polyhedra in danburite match procrystal radii obtained in a structure analysis to within 0.002 Å. The close agreement between these two sets of radii and experimentally determined bonded radii lends credence to Slater's statement that the difference between the electron density distribution observed for a crystal and that calculated for a procrystal (IAM) model of the crystal “would be small and subtle, and very hard to determine by examination of the total charge density.”     

Bioconcentration factors for petroleum hydrocarbons, PAHs, LABs and biogenic hydrocarbons in the blue mussel

Bioconcentration factors (K_bc) for petroleum hydrocarbons, PAHs, LABs and biogenic hydrocarbons in Mytilus edulis were measured in field experiments using time-integrating water samplers. Seven deployments at five sites gave lipid weight K_bcs for total hydrocarbons ranging from 0.99 × 10⁶ to 3.1 × 10⁶ (mean 1.6 × 10⁶)—a narrower range than has been obtained previously. Bioconcentration factors for the PAHs were similar to those for total hydrocarbons where the major hydrocarbon source was oil. However, at other sites the factors for PAHs were an order of magnitude lower than those for petroleum and for hydrocarbons originating from algae. Compositional profiles for the linear alkyl benzenes (LABs) suggested that these compounds were assimilated primarily from the dissolved phase, despite their greater abundance on particles.     

A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.