Distribution and significance of chlorophyll derivatives and oxidation products during the spring phytoplankton bloom in the Celtic Sea April 2002

The abundances and distributions of chlorophyll a and its common transformation products have been profiled by high performance liquid chromatography during the disruption, re-establishment, growth and senescence of a phytoplankton bloom in the Celtic Sea during April 2002. Transformation products of chlorophyll a indicative of herbivory of the phytoplankton bloom have been identified using atmospheric pressure chemical ionisation liquid chromatography-multistage mass spectrometry and chlorophyll oxidation products, formed by autoxidation, are present in increasing abundance in samples collected during the later stages of bloom development. The formation of oxidation products during the earliest stages in the chlorophyll transformation pathway identifies water column processes as sources of these early intermediates in the formation of geologic aetioporphyrins and/or cycloalkanoporphyrins.     

The influence of pH on the kinetics, reversibility and mechanisms of Pb(II) sorption at the calcite-water interface

Pb(II) sorption experiments with calcite powders were conducted in suspensions equilibrated at atmospheric PCO_2(g) and ambient temperature at pH 7.3, 8.2 and 9.4. Pb fractional sorption was low at pH 7.3 and 9.4 relative to pH 8.2, and correlated well with PbCO₃⁰_(aq) speciation. Desorption experiments conducted for initial sorption times ranging from 0.5 h to 12 d reveal an almost completely reversible process at pH 8.2, attributed to the dominance of an adsorption mechanism, with slight and pronounced irreversibility at pH 7.3 and 9.4 respectively. Similarities in X-ray absorption near edge spectra (XANES) for 24 h and 12 d pH 7.3 and 9.4 sorption samples indicate no effect of initial sorption time. Results from linear combination (LC) fits of XANES spectra for samples sorbed at pH 9.4 confirm ∼75% adsorbed and ∼25% coprecipitated components. The coprecipitated fraction was attributed to the non-exchangeable metal observed in desorption experiments. At pH 7.3, ∼95% adsorbed and ∼5% coprecipitated components were obtained. A comparison of results from desorption experiments and LC-XANES alludes to an irreversibly bound adsorbed component for the pH 9.4 12 d sorption sample. Extended X-ray absorption fine structure spectroscopy (EXAFS) analysis of pH 7.3 and 9.4 12 d sorption samples confirms the presence of both adsorbed and coprecipitated metal. At pH 7.3 a first-shell Pb-O bond length of 2.38 Å is intermediate between that of adsorbed (2.34 Å) and coprecipitated (2.51 Å) Pb. At pH 9.4, two first-shell Pb-O distances at 2.35 Å and 2.51 Å were obtained, indicative of the occurrence of both adsorption and coprecipitation and a larger coprecipitated fraction relative to that at pH 7.3, consistent with LC-XANES results. We propose that the disparity in the fraction of coprecipitated metal with pH may be linked to the ability of sorbed Pb to inhibit near-surface dynamic exchange of Ca and CO₃ species, which dictates step advance and retreat. Less effective inhibition of step motion at pH 9.4, due to lower fractional sorption, combined with highest rates of dynamic exchange results in a significant fraction of coprecipitated Pb at this pH. At low pH, though fractional sorption is also low, lower rates of exchange prohibit significant coprecipitation. At pH 8.2, effective inhibition of surface processes due to higher fractional sorption and lower rates of exchange compared to pH 7.3 and 9.4 preclude detectable coprecipitation. Other factors such as changes in surface speciation and solubility of the Pb-Ca solid solution with pH may also come into play. Overall, this study presents evidence for the influence of pH on Pb sorption mechanisms, and addresses the efficiency of Pb immobilization in calcitic systems.     

The Potential for Rural Heritage Tourism in the Clarence Valley of Northern New South Wales

In the past, heritage tourism has been associated with urban sites but there is now an acceptance of the application of this concept to rural areas. In the Clarence Valley in northern New South Wales there is potential for an extension of agritourism associated with working dairy farms to include safari tours to clusters of dairy heritage sites which are scattered throughout the area. Remnants of the old dairy industry, which began in the Clarence River Valley of New South Wales in the late nineteenth century, are scattered throughout the landscape. Over 300 dairy milking bails remain—ghosts of the former thriving industry when over 2000 dairy farms were operating. Concrete foundations of some creameries built in the 1890s can still be found, and three factory buildings still stand. These relics are disappearing quite rapidly and if the importance of the industry is to be recognised by future generations then it seems that some heritage conservation is overdue. At the same time, in order to survive in a post-deregulated economic environment, the remaining 10 dairy farmers in the Clarence Valley are diversifying their activities, with one form of pluriactivity being agritourism. Currently few of these farmers have entered this field but most of them see its potential to broaden their income base. Associated with agritourism at the farm level, the local government authorities see heritage tourism as a way of increasing employment in the region.     

Local thickening of the Cascadia forearc crust and the origin of seismic reflectors in the uppermost mantle

Seismic reflection profiles from three different surveys of the Cascadia forearc are interpreted using P wave velocities and relocated hypocentres, which were both derived from the first arrival travel time inversion of wide-angle seismic data and local earthquakes. The subduction decollement, which is characterized beneath the continental shelf by a reflection of 0.5 s duration, can be traced landward into a large duplex structure in the lower forearc crust near southern Vancouver Island. Beneath Vancouver Island, the roof thrust of the duplex is revealed by a 5–12 km thick zone, identified previously as the E reflectors, and the floor thrust is defined by a short duration reflection from a < 2-km-thick interface at the top of the subducting plate. We show that another zone of reflectors exists east of Vancouver Island that is approximately 8 km thick, and identified as the D reflectors. These overlie the E reflectors; together the two zones define the landward part of the duplex. The combined zones reach depths as great as 50 km. The duplex structure extends for more than 120 km perpendicular to the margin, has an along-strike extent of 80 km, and at depths between 30 km and 50 km the duplex structure correlates with a region of anomalously deep seismicity, where velocities are less than 7000 m s^− 1. We suggest that these relatively low velocities indicate the presence of either crustal rocks from the oceanic plate that have been underplated to the continent or crustal rocks from the forearc that have been transported downward by subduction erosion. The absence of seismicity from within the E reflectors implies that they are significantly weaker than the overlying crust, and the reflectors may be a zone of active ductile shear. In contrast, seismicity in parts of the D reflectors can be interpreted to mean that ductile shearing no longer occurs in the landward part of the duplex. Merging of the D and E reflectors at 42–46 km depth creates reflectivity in the uppermost mantle with a vertical thickness of at least 15 km. We suggest that pervasive reflectivity in the upper mantle elsewhere beneath Puget Sound and the Strait of Georgia arises from similar shear zones.     

Mineralogic variability of the uppermost mantle along mid-ocean ridges

Modal analyses of 273 different peridotites representing 43 dredge stations in the Atlantic, Caribbean, and Indian Oceans define three separate melting trends. Peridotites dredged in the vicinity of “mantle plumes” or hot spots have the most depleted compositions in terms of basaltic components, while peridotites dredged at locations removed from such regions are systematically less depleted. The modal data correlate well with mineral compositions, with the peridotites most depleted in pyroxene also having the most refractory mineral compositions. This demonstrates that they are the probable residues of variable degrees of mantle melting. Further, there is a good correlation between the modal compositions of the peridotites and the major element composition of spatially associated dredged basalts. This demonstrates for the first time that the two must be directly related, as is frequently postulated. The high degree of depletion of the peridotites in basaltic major element components in the vicinity of some documented mantle plumes provides direct evidence for a thermal anomaly in such regions—justifying their frequent designation as “hot spots”. The high incompatible element concentrations in these “plume” basalts, however, are contrary to what is expected for such high degrees of melting, and thus require either selective contributions from locally more abundant enriched veins and/or contamination by a volatile-rich metasomatic front from depth.     

Reconstructing the ancestral Yellowstone plume from accreted seamounts and its relationship to flat-slab subduction

Recent geodynamic analyses have emphasized the relationship between modern flat-slab subduction zones and the overriding of buoyant oceanic crust. Although most models for the evolution of the Late Mesozoic–Cenozoic Laramide orogeny in the southwestern United States involve flat-slab subduction, the mechanisms proposed are controversial. An examination of the geological evolution of the 60–50-Ma Crescent terrane of the Coast Ranges indicates that it was formed in a shallowing-upward Loihi-type oceanic setting culminating in the eruption of subaerial lavas. Plate reconstructions indicate that the Crescent terrane was emplaced into ca. 20-Ma crust, and the presence of subaerial lavas implies an uplift due to the plume of ca. 4.2 km, which we use to calculate a minimum buoyancy flux of 1.1 Mg s⁻¹, similar to that of the modern Yellowstone plume.Published paleomagnetic data indicate that the Crescent terrane was formed at a paleolatitude similar to that of the Yellowstone plume. The Crescent seamount was accreted within 5 My of the cessation of plume magmatism. Plate reconstructions indicate that it would have originated about 750 km to the west of the North American plate margin if it developed above a fixed Yellowstone plume, and are therefore consistent with the recorded very short interval between its formation and tectonic emplacement.We interpret the Crescent terrane as due to the ancestral Yellowstone plume. Such a plume would have generated an elongate swell and related plateau that would have been overridden by the North American margin. Taken together, the relationship between flat-slab and overriding of oceanic plateau in Laramide times would have been analogous to the relationship between modern Andean flat-slab subduction zones and the Juan Fernandez and Nazca oceanic plateaus.     

Tethyan, Mediterranean, and Pacific analogues for the Neoproterozoic–Paleozoic birth and development of peri-Gondwanan terranes and their transfer to Laurentia and Laurussia

Modern Tethyan, Mediterranean, and Pacific analogues are considered for several Appalachian, Caledonian, and Variscan terranes (Carolina, West and East Avalonia, Oaxaquia, Chortis, Maya, Suwannee, and Cadomia) that originated along the northern margin of Neoproterozoic Gondwana. These terranes record a protracted geological history that includes: (1) 1 Ga (Carolina, Avalonia, Oaxaquia, Chortis, and Suwannee) or 2 Ga (Cadomia) basement; (2) 750–600 Ma arc magmatism that diachronously switched to rift magmatism between 590 and 540 Ma, accompanied by development of rift basins and core complexes, in the absence of collisional orogenesis; (3) latest Neoproterozoic–Cambrian separation of Avalonia and Carolina from Gondwana leading to faunal endemism and the development of bordering passive margins; (4) Ordovician transport of Avalonia and Carolina across Iapetus terminating in Late Ordovician–Early Silurian accretion to the eastern Laurentian margin followed by dispersion along this margin; (5) Siluro-Devonian transfer of Cadomia across the Rheic Ocean; and (6) Permo-Carboniferous transfer of Oaxaquia, Chortis, Maya, and Suwannee during the amalgamation of Pangea. Three potential models are provided by more recent tectonic analogues: (1) an “accordion” model based on the orthogonal opening and closing of Alpine Tethys and the Mediterranean; (2) a “bulldozer” model based on forward-modelling of Australia during which oceanic plateaus are dispersed along the Australian plate margin; and (3) a “Baja” model based on the Pacific margin of North America where the diachronous replacement of subduction by transform faulting as a result of ridge–trench collision has been followed by rifting and the transfer of Baja California to the Pacific Plate. Future transport and accretion along the western Laurentian margin may mimic that of Baja British Columbia. Present geological data for Avalonia and Carolina favour a transition from a “Baja” model to a “bulldozer” model. By analogy with the eastern Pacific, we name the oceanic plates off northern Gondwana: Merlin (≡Farallon), Morgana (≡Pacific), and Mordred (≡Kula). If Neoproterozoic subduction was towards Gondwana, application of this combined model requires a total rotation of East Avalonia and Carolina through 180° either during separation (using a western Transverse Ranges model), during accretion (using a Baja British Columbia “train wreck” model), or during dispersion (using an Australia “bulldozer” model). On the other hand, Siluro-Devonian orthogonal transfer (“accordion” model) from northern Africa to southern Laurussia followed by a Carboniferous “Baja” model appears to best fit the existing data for Cadomia. Finally, Oaxaquia, Chortis, Maya, and Suwannee appear to have been transported along the margin of Gondwana until it collided with southern Laurentia on whose margin they were stranded following the breakup of Pangea. Forward modeling of a closing Mediterranean followed by breakup on the African margin may provide a modern analogue. These actualistic models differ in their dictates on the initial distribution of the peri-Gondwanan terranes and can be tested by comparing features of the modern analogues with their ancient tectonic counterparts.     

Timing of magma extraction during the Campanian Ignimbrite eruption (Campi Flegrei Caldera)

A core drilled within the northern part of the city of Napoli has offered the unique opportunity to observe in one single sequence the superposition of the four pyroclastic flow units emplaced during the Campanian Ignimbrite (CI) eruption. Such a stratigraphic succession has never been encountered before in natural or in man made exposures. Therefore the CI sequence was reconstructed only on the basis of stratigraphic correlations and compositional data (in literature). The occurrence of four superposed CI flows, together with all the data available (in literature) allowed us to better constrain the chemical stratigraphy of the deposit and the compositional structure of the CI magma chamber. The CI magma chamber includes two cogenetic magma layers, separated by a compositional gap. The upper magma layer was contaminated by interaction with radiogenic fluids. The two magma layers were extruded either individually or simultaneously during the course of the eruption. In the latter case they produced a hybrid magma. But no evidence of input of new geochemically and isotopically distinct magma batches just prior or during the eruption has been found. Comparison with the exposed CI deposits has permitted reconstruction of variable eruption phases and related magma withdrawal and caldera collapse episodes. The eruption was likely to have began with phreatomagmatic explosions followed by the formation of a sustained plinian eruption column fed by the simultaneous extraction from both magma layers. Towards the end of this phase the upward migration of the fragmentation surface and the decrease in magma eruption rate and/or activation of fractures formed an unstable pulsating column that was fed only by the most-evolved magma layer. This plinian phase was followed by the collapse of the eruption column and the beginning of caldera formation. At this stage expanded pyroclastic flows fed by the upper magma layer in the chamber generated. During the following major caldera collapse episode, the maximum mass discharge rate was reached and both magma layers were tapped, generating expanded pyroclastic flows. Towards the end of the eruption, only the deeper and less differentiated magma layer was tapped producing more concentrated pyroclastic flows that traveled short distances.     

Origin and significance of 13-hydroxychlorophyll derivatives in sediments

The authenticity of hydroxychlorophyll derivatives in sediments has been verified by subjecting pure chlorophyll preparations to the extraction method used for sediments. Model studies of chlorophyll autoxidation reveal hydroxychlorophyll as the major product formed in the presence of hydrogen peroxide. Its stability to further oxidation implies that hydroxychlorophyll derivatives are not precursors of aetioporphyrins and are more likely to produce cycloalkanoporphyrins via the processes of diagenesis. The occurrence of 13²-hydroxyphaeophytin a throughout a sediment core from Loch Ness confirms it to be a widespread chlorophyll oxidation product formed during early diagenesis. Profiles of hydroxychlorophyll derivatives in a sediment core from an Antarctic lake demonstrate their potential for use as markers of oxidation processes in palaeoenvironmental assessment.