The biogeochemical sulfur cycle in the marine boundary layer over the Northeast Pacific Ocean

The major components of the marine boundary layer biogeochemical sulfur cycle were measured simultaneously onshore and off the coast of Washington State, U.S.A. during May 1987. Seawater dimethylsulfide (DMS) concentrations on the continental shelf were strongly influenced by coastal upwelling. Concentration further offshore were typical of summer values (2.2 nmol/L) at this latitude. Although seawater DMS concentrations were high on the biologically productive continental shelf (2–12 nmol/L), this region had no measurable effect on atmospheric DMS concentrations. Atmospheric DMS concentrations (0.1–12 nmol/m³), however, were extremely dependent upon wind speed and boundary layer height. Although there appeared to be an appreciable input of non-sea-salt sulfate to the marine boundary layer from the free troposphere, the local flux of DMS from the ocean to the atmosphere was sufficient to balance the remainder of the sulfur budget.     

Compositional Zoning of the Bishop Tuff

Compositional data for >400 pumice clasts, organized accordingto eruptive sequence, crystal content, and texture, providenew perspectives on eruption and pre-eruptive evolution of the>600 km³ of zoned rhyolitic magma ejected as the Bishop Tuffduring formation of Long Valley caldera. Proportions and compositionsof different pumice types are given for each ignimbrite packageand for the intercalated plinian pumice-fall layers that eruptedsynchronously. Although withdrawal of the zoned magma was lesssystematic than previously realized, the overall sequence displaystrends toward greater proportions of less evolved pumice, morecrystals (0·5–24 wt %), and higher FeTi-oxide temperatures(714–818°C). No significant hiatus took place duringthe 6 day eruption of the Bishop Tuff, nearly all of which issuedfrom an integrated, zoned, unitary reservoir. Shortly beforeeruption, however, the zoned melt-dominant portion of the chamberwas invaded by batches of disparate lower-silica rhyolite magma,poorer in crystals than most of the resident magma but slightlyhotter and richer in Ba, Sr, and Ti. Interaction with residentmagma at the deepest levels tapped promoted growth of Ti-richrims on quartz, Ba-rich rims on sanidine, and entrapment ofnear-rim melt inclusions relatively enriched in Ba and CO₂.Varied amounts of mingling, even in higher parts of the chamber,led to the dark gray and swirly crystal-poor pumices sparselypresent in all ash-flow packages. As shown by FeTi-oxide geothermometry,the zoned rhyolitic chamber was hottest where crystal-richest,rendering any model of solidification fronts at the walls orroof unlikely. The main compositional gradient (75–195ppm Rb; 0·8–2·2 ppm Ta; 71–154 ppmZr; 0·40–1·73% FeO*) existed in the melt,prior to crystallization of the phenocryst suite observed, whichincluded zircon as much as 100 kyr older than the eruption.The compositions of crystals, though themselves largely unzoned,generally reflect magma temperature and the bulk compositionalgradient, implying both that few crystals settled or were transportedfar and that the observed crystals contributed little to establishingthat gradient. Upward increases in aqueous gas and dissolvedwater, combined with the adiabatic gradient (for the 5 km depthrange tapped) and the roofward decline in liquidus temperatureof the zoned melt, prevented significant crystallization againstthe roof, consistent with dominance of crystal-poor magma earlyin the eruption and lack of any roof-rind fragments among theBishop ejecta, before or after onset of caldera collapse. Amodel of secular incremental zoning is advanced wherein numerousbatches of crystal-poor melt were released from a mush zone(many kilometers thick) that floored the accumulating rhyoliticmelt-rich body. Each batch rose to its own appropriate levelin the melt-buoyancy gradient, which was self-sustaining againstwholesale convective re-homogenization, while the thick mushzone below buffered it against disruption by the deeper (non-rhyolitic)recharge that augmented the mush zone and thermally sustainedthe whole magma chamber. Crystal–melt fractionation wasthe dominant zoning process, but it took place not principallyin the shallow melt-rich body but mostly in the pluton-scalemush zone before and during batchwise melt extraction. KEY WORDS: Bishop Tuff; ignimbrite; magma zonation; mush model; rhyolite     

Measurement of stress effects (scope for growth) and contaminant levels in mussels (Mytilus edulis) collected from the Irish Sea

The objective of this research was to quantify the impact of pollution along the coastlines of the Irish Sea. Pollution assessment was based on the combined measurement of scope for growth (SFG), and chemical contaminants in the tissues of mussels (Mytilus edulis) collected from 38 coastal sites around the Irish Sea during June-July in 1996 and 1997. On the UK mainland coast, the SFG showed a general trend with a significant decline in water quality in the Liverpool and Morecambe Bay region. High water quality was recorded along the west coast of Wales, as well as southwest England and northwest Scotland (clean reference sites outside the Irish Sea). Along the coast of Ireland there was a similar trend with reduced SFG within the Irish Sea region. SFG was generally low north of Duncannon and then improved north of Belfast. The poor water quality on both sides of the Irish Sea is consistent with the prevailing hydrodynamics and the spatial distribution of contaminants associated with urban/ industrial development. The decline in SFG of mussels on both sides of the Irish Sea was associated with a general increase in contaminant levels in the mussels. Certain contaminants, including PAHs, TBT, sigmaDDT, Dieldrin, gamma-HCH, PCBs, and a few of the metals (Cd, Se, Ag, Pb), showed elevated concentrations. Many of these contaminants were particularly elevated in the coastal margins of Liverpool Bay, Morecambe Bay and Dublin Bay. A quantitative toxicological interpretation (QTI) of the combined tissue residue chemistry and SFG measurements indicated that at the majority of coastal sites, c. 50 to > 80% of the observed decline in SFG was due to PAHs as a result of fossil fuel combustion and oil spills. TBT levels were highest at major ports and harbours, but these concentrations only made a minor contribution to the overall reduction in SFG. At no sites were individual metals accumulated to concentrations that could cause a significant effect on SFG. The study identified many sites where the observed reduction in SFG was far greater than predicted from the limited number of chemical contaminants analysed, thus indicating the presence of additional 'unknown toxicants'. Sewage (containing domestic, agricultural and industrial components) appears to be an important contributor to reduced SFG and linear alkylbenzenes (LABs) and As may provide suitable 'sewage markers'. There was a highly significant positive correlation between SFG and As (P < 0.001). This relationship may be due to reduced As uptake by algal food material and mussels at sites with elevated P04 concentrations (e.g. at sites with sewage inputs). Phosphate is a known competitive inhibitor of As accumulation, at least in algae. The results highlight that further research is required on 'sewage markers' in mussels. The SFG approach therefore provides a rapid, cost-effective and quantitative measure of pollution impact, as well as a means of identifying the causes through a QTI of tissue contaminants levels. It also serves to identify the presence of unidentified toxicants and areas that require further study.     

Silica depleted melting of pelites. Petrogenetic grid and application to the Susqueda Aureole, Spain

Metapelitic rocks in the low pressure contact metamorphic aureole around the Susqueda igneous complex, Spain show a number of features that make them an ideal testing ground for the modelling of silica‐undersaturated melting. Rocks in the aureole experienced localized depletion in silica by the segregation of quartz veins during a pre‐anatectic, regional cordierite‐andalusite grade metamorphic event. These rocks were then intruded by gabbroic to dioritic rocks of the Susqueda igneous complex that formed a migmatitic contact metamorphic aureole in the country rocks. This migmatisation event caused quartz‐saturated hornfels and restite formation in rocks that had experienced no quartz vein segregation in the previous regional metamorphic event, but silica‐undersaturated melting in those rocks that were previously depleted in silica. Silica‐undersaturated melting is investigated using a new petrogenetic P–T projection and equilibrium pseudosections calculated in the KFMASH and NCKFMASH systems, respectively. The grid considers quartz absent equilibria and a range of phases that form typically in silica‐undersaturated bulk compositions, for example corundum. It is shown that the quartz‐rich precursors in the Susqueda contact aureole produced about 10% melt during contact metamorphism. However, most of this melt was extracted leaving behind rocks with restitic bulk compositions and minor leucosome segregation. It is suggested that the melt mixed with the host igneous rocks causing an apparent magmatic zoning from diorite in the centre of the complex to tonalite at the margins. In contrast, the quartz‐poor precursors (from which the quartz veins segregated) melted in the silica‐undersaturated field producing a range of assemblages including peritectic corundum and spinel. Melting of the silica‐undersaturated rocks produced only negligible melt and no subsequent melt loss.     

Al,Si ordering in cordierite using “magic angle spinning” NMR

A method of determining the number of Al-O-Al bonds per unit cell from ²⁹Si nuclear magnetic resonance (NMR) data of synthetic cordierites with increasing Si, Al order is described. The number of Al-O-Al bonds is found to vary linearly with the logarithm of the annealing time. This may be correlated with previously published heat of solution data on similar samples (Carpenter et al. 1983) to determine the enthalpy change Δh, associated with a single Al?Si interchange in cordierite. Δh is found to be 8.1 kcal/mole. The NMR data show that the short range Al, Si order cannot be described in terms of twin domains of ordered orthorhombic cordierite. An ordering model derived from group theoretical constraints on possible Al, Si distributions within the hexagonal symmetry of the cordierite is found to provide a better fit to the NMR data.     

Coupled changes in sand grain size and sand transport driven by changes in the upstream supply of sand in the Colorado River: Relative importance of changes in bed-sand grain size and bed-sand area

Sand transport in the Colorado River in Marble and Grand canyons was naturally limited by the upstream supply of sand. Prior to the 1963 closure of Glen Canyon Dam, the river exhibited the following four effects of sand supply limitation: (1) hysteresis in sediment concentration, (2) hysteresis in sediment grain size coupled to the hysteresis in sediment concentration, (3) production of inversely graded flood deposits, and (4) development or modification of a lag between the time of a flood peak and the time of either maximum or minimum (depending on reach geometry) bed elevation. Construction and operation of the dam has enhanced the degree to which the first two of these four effects are evident, and has not affected the degree to which the last two effects of sand supply limitation are evident in the Colorado River in Marble and Grand canyons. The first three of the effects involve coupled changes in suspended-sand concentration and grain size that are controlled by changes in the upstream supply of sand. During tributary floods, sand on the bed of the Colorado River fines; this causes the suspended sand to fine and the suspended-sand concentration to increase, even when the discharge of water remains constant. Subsequently, the bed is winnowed of finer sand, the suspended sand coarsens, and the suspended-sand concentration decreases independently of discharge. Also associated with these changes in sand supply are changes in the fraction of the bed that is covered by sand. Thus, suspended-sand concentration in the Colorado River is likely regulated by both changes in the bed-sand grain size and changes in the bed-sand area. A physically based flow and suspended-sediment transport model is developed, tested, and applied to data from the Colorado River to evaluate the relative importance of changes in the bed-sand grain size and changes in the bed-sand area in regulating suspended-sand concentration. Although the model was developed using approximations for steady, uniform flow, and other simplifications that are not met in the Colorado River, the results nevertheless support the idea that changes in bed-sand grain size are much more important than changes in bed-sand area in regulating the concentration of suspended sand.     

The geometry and petrogenesis of hydrothermal dolomites at Navan, Ireland

The dolomites at Navan, Ireland, formed in Courceyan peritidal and shallow-shelf limestones. The dolomite body has a plume-like geometry, cross-cutting both lithological boundaries and diagenetic barriers generated by sea-floor cementation and emergence. The dolomitizing fluids rose parallel to major faults to diffuse laterally through the succession, controlled by variations in permeability that reflect both facies variation on deposition and pre-dolomitization diagenesis. Cathodoluminescent zones reveal three principal stages of dolomite emplacement, separated by dissolution surfaces, with each stage reflecting several changes in the character of dolomitizing solutions. The predominance of dull zones indicates burial rather than surface conditions. The dolomites formed some time after burial in response to an areally limited hydrothermally-driven flow. Isotope values (σ¹⁸O of — 6σ6 to — 10.4%_δ and σ¹³C of — 0σ2 to +2σ5%_δ PDB), and fluid inclusion data, suggest that these fluids had compositions similar to those of Carboniferous seawater. However, these became hotter with time, with temperature increasing from 60 to 160δC. The Navan dolomites are closely associated with Europe's largest zinc-lead deposit. The distribution of the ores follows the same trend as that of the dolomites and paragenetic relationships indicate that dolomitization and mineralization were temporally and genetically related.     

The gravitational field of topographic-isostatic masses and the hypothesis of mass condensation II-the topographic-isostatic geoid

In Part I we focussed on a convergent representation of the gravitational potential generated bytopographic masses on top of the equipotential surface atMean Sea Level, thegeoid, and by those masses which compensate topography. Topographic masses have also been condensated, namely represented by a single layer. Part II extends the computation of the gravitational field of topographic-isostatic masses by a detailed analysis of itsforce field in terms ofvector-spherical harmonic functions. In addition, the discontinuous mass-condensated topographic gravitational force vector (head force) is given. Once we identify theMoho discontinuity asone interface of isostatically compensated topographical masses, we have computed the topographic potential and the gravitational potential which is generated by isostatically compensated masses atMean Sea Level, the geoid, and illustrated by various figures of geoidal undulations. In comparison to a data oriented global geoid computation ofJ. Engels (1991) the conclusion can be made that the assumption of aconstant crustal mass density, the basic condition for isostatic modeling, does not apply. Insteaddensity variations in the crust, e.g. betweenoceanic and continental crust densities, have to be introduced in order to match the global real geoid and its topographic-isostatic model. The performed analysis documents that thestandard isostatic models based upon aconstant crustal density areunreal.     

Pillow talk

Three distinct types of pillows and pillow lava sequences with different modes of origin have been recognized in the extrusive sequences comprising the upper parts of ophiolite complexes that represent the mafic portion of the floor of an Early Cretaceous back-arc basin in southern Chile. One type of pillow formed by non-explosive submarine effusion. A second type formed by magmatic intrusion into pre-existing aquagene tuff formed by explosive eruption. The third type of pillow occurs within dikes, forming pillowed dikes, possibly as a result of vapor streaming within a cooling dike. Where studied in southern Chile, aquagene tuffs and intrusive pillows decrease and water-lain pillows increase in relative abundance from north to south. This variation corresponds with a north-to-south decrease in both the relative volume of extrusives to extensional dikes and the range and volume of differentiated rocks, suggesting a southward increase in rate of extension relative to rate of magma supply within the spreading ridges at which the ophiolites formed. In the northern part of the original basin where the rate of extension was small relative to the rate of magma supply, magma remained in magma chambers longer, resulting in a greater range and volume of differentiated rocks. The larger volume of more differentiated, cooler and more viscous magmas, in conjunction with the likelihood of more violent eruption of volatile-rich differentiates, may have been responsible for the large volume of aquagene tuff in the northern part of the original basin. These observations in southern Chile suggest that ophiolites which contain a great abundance of aquagene tuffs and intrusive pillow lavas formed in tectonic environments in which the rate of extension was small relative to the rate of magma supply (island arcs, embryonic marginal basins). Ophiolites with predominantly water-lain pillowed and massive lavas formed in tectonic environments in which the rate of extension was large relative to the rate of magma supply (mid-ocean ridges, mature back-arc basins). Thus geologic field data may supplement geochemical data as a tool in distinguishing the original igneous-tectonic environments in which ophiolites originate.     

Structure Function Analysis of Two-Scale Scalar Ramps. Part II: Ramp Characteristics and Surface Renewal Flux Estimation

Ramp features in the turbulent scalar field are associated with turbulent coherent structures, which dominate energy and mass fluxes in the atmospheric surface layer. Although finer scale ramp-like shapes embedded within larger scale ramp-like shapes can readily be perceived in turbulent scalar traces, their presence has largely been overlooked in the literature. We demonstrate the signature of more than one ramp scale in structure functions of the turbulent scalar field measured from above bare ground and two types of short plant canopies, using structure-function time lags ranging in scale from isotropic to larger than the characteristic coherent structures. Spectral analysis of structure functions was used to characterize different scales of turbulent structures. By expanding structure function analysis to include two ramp scales, we characterized the intermittency, duration, and surface renewal flux contribution of the smallest (i.e., Scale One) and the dominant (i.e., Scale Two) coherent structure scales. The frequencies of the coherent structure scales increase with mean wind shear, implying that both Scale One and Scale Two are shear-driven. The embedded Scale One turbulent structure scale is ineffectual in the surface-layer energy and mass transport process. The new method reported here for obtaining surface renewal-based scalar exchange works well over bare ground and short canopies under unstable conditions, effectively eliminating the α calibration for these conditions and forming the foundation for analysis over taller and more complex surfaces.