Ultrastructure, aggregation-state, and crystal growth of biogenic nanocrystalline sphalerite and wurtzite

In this study, we investigated the size, submicrometer-scale structure, and aggregation state of ZnS formed by sulfate-reducing bacteria (SRB) in a SRB-dominated biofilm growing on degraded wood in cold (Tsimilar to8degreesC), circumneutral-pH (7.2-8.5) waters draining from an abandoned, carbonate-hosted Pb-Zn mine. High-resolution transmission electron microscope (HRTEM) data reveal that the earliest biologically induced precipitates are crystalline ZnS nanoparticles 1-5 nm in diameter. Although most nanocrystals have the sphalerite structure, nanocrystals of wurtzite are also present, consistent with a predicted size dependence for ZnS phase stability. Nearly all the nanocrystals are concentrated into 1-5 mum diameter spheroidal aggregates that display concentric banding patterns indicative of episodic precipitation and flocculation. Abundant disordered stacking sequences and faceted, porous crystal-aggregate morphologies are consistent with aggregation-driven growth of ZnS nanocrystals prior to and/or during spheroid formation. Spheroids are typically coated by organic polymers or associated with microbial cellular surfaces, and are concentrated roughly into layers within the biofilm. Size, shape, structure, degree of crystallinity, and polymer associations will all impact ZnS solubility, aggregation and coarsening behavior, transport in groundwater, and potential for deposition by sedimentation. Results presented here reveal nanometer- to micrometer-scale attributes of biologically induced ZnS formation likely to be relevant to sequestration via bacterial sulfate reduction (BSR) of other potential contaminant metal(loid)s, such as Pb2+, Cd2+, As3+ and Hg2+, into metal sulfides. The results highlight the importance of basic mineralogical information for accurate prediction and monitoring of long-term contaminant metal mobility and bioavailability in natural and constructed bioremediation systems. Our observations also provoke interesting questions regarding the role of size-dependent phase stability in biomineralization and provide new insights into the origin of submicrometer- to millimeter-scale petrographic features observed in low-temperature sedimentary sulfide ore deposits.

Biogeographic analysis of jurassic-early cretaceous wood assemblages from Gondwana

The terrestrial biogeography of Gondwana during Jurassic-Early Cretaceous times is poorly resolved, and the flora is usually considered to have been rather uniform. This is surprising given the size of Gondwana, which extended from the equator to the South Pole. Documenting Gondwanan terrestrial floristic provincialism in the Jurassic-Early Cretaceous times is important because it provides a historical biogeographic context in which to understand the tremendous evolutionary radiations that occurred during the mid-Cretaceous. In this paper, the distribution of Jurassic-Early Cretaceous fossil wood is analysed at generic level across the entire supercontinent. Specifically, wood assemblages are analyzed in terms of five climatic zones (summer wet, desert, winter wet, warm temperate, cool temperate) established on the basis of independent data. Results demonstrate that araucarian-like conifer wood was a dominant, cosmopolitan element, whereas other taxa showed a greater degree of provincialism. Indeed, several narrowly endemic morphogenera are recognizable from the data. Finally, comparisons with Laurasian wood assemblages indicate strong parallelism between the vegetation of both hemispheres. (C) 2004 Elsevier B.V. All rights reserved.

Early-Middle Jurassic stratigraphy of the Fortrose-Chaslands region, southernmost South Island, New Zealand

The 40 km of coastline from Fortrose to Chaslands Mistake (southeastern South Island, New Zealand) comprises sediments that are part of the Early-Middle Jurassic of the Murihiku Terrane. The sediments are dominantly fluvial with some marine beds and alluvial fan deposition, and display an evolution of fluvial style which progresses from perennial flow to seasonal flow. The McPhee Cove Conglomerate is a prominent unit to the north. It has been used to separate two formations which would otherwise, on inherent lithological grounds, be difficult to distinguish. This paper discusses several similar conglomerates which occur in the south, but which are separated from the type area of the McPhee Conglomerate by major tectonic disruption. Hence, the existing lithostratigraphic nomenclature to the north, including the McPhee Cove Conglomerate, cannot be simply extended southwards. The Fortrose-Chaslands area appears to consist of two tectonic blocks, the Slope Point Block and the Brothers Block, which are separated from each other and from the adjacent Papatowai Block by major strike faults (or fault zones). A change is proposed to the existing stratigraphy which involves recognising all terrestrial sediments as part of the False Island Formation. Four prominent clast-supported conglomerate horizons are named as members of the False Islet Formation: the White Head Conglomerate, Black Bluff Conglomerate. Hoiho Conglomerate, and Slope Point Conglomerate Members. The latter contains five named conglomerate beds.

ELA-ICP-MS U-Pb zircon geochronology of regional volcanism hosting the Bajo de la Alumbrera Cu-Au deposit: implications for porphyry-related mineralization

ELA-ICP-MS U-Pb zircon geochronology has been used to show that the porphyritic intrusions related to the formation of the Bajo de la Alumbrera porphyry Cu-Au deposit, NW Argentina, are cogenetic with stratigraphically well-constrained volcanic and volcaniclastic rocks of the Late Miocene Farallon Negro Volcanic Complex. Zircon geochronology for intrusions in this deposit and the host volcanic sequence show that multiple mineralized porphyries were emplaced in a volcanic complex that developed over 1.5 million years. Volcanism occurred in a multivent volcanic complex in a siliciclastic intermontane basin. The complex evolved from early mafic-intermediate effusive phases to a later silicic explosive phase associated with mafic intrusions. Zircons from the basal mafic-intermediate lavas have ages that range from 8.46 +/- 0.14 to 7.94 +/- 0.27 Ma. Regionally extensive silicic explosive volcanism occurred at similar to8.0 Ma (8.05 +/- 0.13 and 7.96 +/- 0.11 Ma), which is co-temporal with intrusion of the earliest mineralized porphyries at Bajo de la Alumbrera (8.02 +/- 0.14 and 7.98 +/- 0.14 Ma). Regional uplift and erosion followed during which the magmatic-hydrothermal system was probably unroofed. Shortly thereafter, dacitic lava domes were extruded (7.95 +/- 0.17 Ma) and rhyolitic diatremes (7.79 +/- 0.13 Ma) deposited thick tuff blankets, across the region. Emplacement of large intermediate composition stocks occurred at 7.37 +/- 0.22 Ma, shortly before renewed magmatism occurred at Bajo de la Alumbrera (7.10 +/- 0.07 Ma). The latest porphyry intrusive event is temporally associated with new ore-bearing magmatic-hydrothermal fluids. Other dacitic intrusions are associated with subeconomic deposits that formed synchronously with the mineralized porphyries at Bajo de la Alumbrera. However, their emplacement continued (from 7.10 +/- 0.06 to 6.93 +/- 0.07 Ma) after the final intrusion at Bajo de al Alumbrera. Regional volcanism had ceased by 6.8 Ma (6.92 +/- 0.07 Ma). The brief history of the volcanic complex hosting the Bajo de la Alumbrera Cu-Au deposit differs from that of other Andean provinces hosting porphyry deposits. For example, at the El Salvador porphyry copper district in Chile, magmatism related to Cu mineralization was episodic in regional igneous activity that occurred over tens of millions of years. Bajo de la Alumbrera resulted from the superposition of multiple porphyry-related hydrothermal systems, temporally separated by a million years. It appears that the metal budget in porphyry ore deposits is not simply a function of their longevity and/or the superposition of multiple porphyry systems. Nor is it a function of the duration of the associated cycle of magmatism. Instead, the timing of processes operating in the parental magma body is the controlling factor in the formation of a fertile porphyry-related ore system.

The igneous charnockite—high-K alkali-calcic I-type granite—incipient charnockite association in Trivandrum Block, southern India

The Pan-African (640 Ma) Chengannoor granite intrudes the NW margin of the Neoproterozoic high-grade metamorphic terrain of the Trivandrum Block (TB), southern India, and is spatially associated with the Cardamom hills igneous charnockite massif (CM). Geochemical features characterize the Chengannoor granite as high-K alkali-calcic I-type granite. Within the constraints imposed by the high temperature, anhydrous, K-rich nature of the magmas, comparison with recent experimental studies on various granitold source compositions, and trace- and rare-earth-element modelling, the distinctive features of the Chengannoor granite reflect a source rock of igneous charnockitic nature. A petrogenetic model is proposed whereby there was a period of basaltic underplating; the partial melting of this basaltic lower crust formed the CM charnockites. The Chengannoor granite was produced by the partial melting of the charnoenderbites from the CM, with subsequent fractionation dominated by feldspars. In a regional context, the Chengannoor I-type granite is considered as a possible heat source for the near-UHT nature of metamorphism in the northern part of the TB. This is different from previous studies, which favoured CM charnockite as the major heat source. The Occurrence of incipient charnockites (both large scale as well as small scale) adjacent to the granite as well as pegmatites (which contain CO2, CO2-H2O, F and other volatiles), suggests that the fluids expelled from the alkaline magma upon solidification generated incipient charnockites through fluid-induced lowering of water activity. Thus the granite and associated alkaline pegmatites acted as conduits for the transfer of heat and volatiles in the Achankovil Shear Zone area, causing pervasive as well as patchy charnockite formation. The transport Of CO2 by felsic melts through the southern Indian middle crust is suggested to be part of a crustal-scale fluid system that linked mantle heat and CO2 input with upward migration of crustally derived felsic melts and incipient charnockite formation, resulting in an igneous charnockite - I-type granite - incipient charnockite association.

Spatio-temporal scanning and statistical test of the accelerating moment release (AMR) model using Australian earthquake data

The Accelerating Moment Release (AMR) preceding earthquakes with magnitude above 5 in Australia that occurred during the last 20 years was analyzed to test the Critical Point Hypothesis. Twelve earthquakes in the catalog were chosen based on a criterion for the number of nearby events. Results show that seven sequences with numerous events recorded leading up to the main earthquake exhibited accelerating moment release. Two occurred near in time and space to other earthquakes preceded by AM R. The remaining three sequences had very few events in the catalog so the lack of AMR detected in the analysis may be related to catalog incompleteness. Spatio-temporal scanning of AMR parameters shows that 80% of the areas in which AMR occurred experienced large events. In areas of similar background seismicity with no large events, 10 out of 12 cases exhibit no AMR, and two others are false alarms where AMR was observed but no large event followed. The relationship between AMR and Load-Unload Response Ratio (LURR) was studied. Both methods predict similar critical region sizes, however, the critical point time using AMR is slightly earlier than the time of the critical point LURR anomaly.

Fossil biotas from the Okanagan Highlands, southern British Columbia and northeastern Washington State: climates and ecosystems across an Eocene landscape

The late Early to early Middle Eocene Okanagan Highlands fossil sites, spanning -1000 km north-south (northeastern Washington State, southern British Columbia) provide an opportunity to reconstruct biotic communities across a broad upland landscape during the warmest part of the Cenozoic. Plant taxa from these fossil sites are characteristic of the modern eastern North American deciduous forest zone, principally the mixed mesophytic forest, but also include extinct taxa, taxa known only from eastern Asian mesothermal forests, and a small number of taxa restricted to the present-day North American west coast coniferous biome. In this preliminary report, paleoclimates and forest types are reconstructed using collections from Republic in Washington State, USA., and Princeton, Quilchena, Falkland, McAbee, Hat Creek, Horsefly, and Driftwood Canyon in British Columbia, Canada. Both leaf margin analysis (LMA) and quantitative bioclimatic analysis of identified nearest living relatives of megaflora indicated upper microthermal to lower mesothermal moist environments (MAT -10-15 degrees C, CMMT > 0 degrees C, MAP > 100 cm/year). Some taxa common to most sites suggest cool conditions (e.g., Abies, other Pinaceae; Alnus, other Betulaceae). However, all floras contain a substantive broadleaf deciduous element (e.g., Fagaceae, Juglandaceae) and conifers (e.g., Metasequoia) with the bioclimatic analysis yielding slightly higher MAT than LMA. Thermophilic (principally mesothermal) taxa include various insects, the aquatic fern Azolla, palms, the banana relative Ensete, taxodiaceous conifers, Eucommia and Gordonia, taxa which may have occurred near their climatic limits. The mixture of thermophilic and temperate insect and plant taxa indicates low-temperature seasonality (i.e., highly equable climate).

Heat-induced and other chemical changes in commercial UHT milks

The properties of commercial directly and indirectly heated UHT milks, both after heating and during storage at room temperature for 24 weeks, were studied. Thermally induced changes were examined by changes in lactulose, furosine and acid-soluble whey proteins. The results confirmed previous reports that directly heated UHT milks suffer less heat damage than indirectly heated milk. During storage, furosine increased and bovine serum albumin in directly heat-treated milks decreased significantly. The changes in lactulose, alpha-lactalbumin and beta-lactoglobulin were not statistically significant. The data suggest that heat treatment indicators should be measured as soon as possible after processing to avoid any misinterpretations of the intensity of the heat treatment.

A new estimate for the composition of weathered young upper continental crust from alluvial sediments, Queensland, Australia

We present new major element, trace element and Nd-isotope data for 30 alluvial sediments collected from 25 rivers in Queensland, E Australia. Samples were chosen to represent drainage from the region's most important lithologies, including Tertiary intraplate volcanic rocks, a Cretaceous igneous province (and sedimentary rocks derived thereof) as well as Proterozoic blocks. In most chemical and isotopic aspects, the alluvial sediments represent binary or ternary mixing relationships, with absolute abundances implied to reflect the proportion of lithologies in the catchments. When averaged, the studied sediments differ from other proxies of upper continental crust (UCC) mainly in their relative middle rare earth element enrichment (including an elevated Sm/Nd ratio), higher relative Eu abundance and higher Nb/Ta ratio. These features are inherited from eroded Tertiary intraplate basalts, which commonly form topographic highs in the studied region. Despite the high degree of weathering strong to excellent coherence between similarly incompatible elements is found for all samples. From this coherence, we suggest revisions of the following upper crustal element ratios: Y/Ho = 26.2, Yb/Tm = 6.37, Th/W = 7.14, Th/Tl = 24 and Zr/Hf = 36.9. Lithium, Rb, Cs and Be contents do not seem depleted relative to UCC, which may reflect paucity of K-feldspar in the eroded catchments. Nickel, Cr, Pb, Cu and Zn concentrations are elevated in polluted rivers surrounding the state capital. River sediments in the Proterozoic Georgetown Inlier are elevated in Pb, Cu and Zn but this could be a natural phenomenon reflecting abundant sulphide mineralisation in the area. Except for relative Sr concentrations, which broadly anticorrelate with mean annual rainfall in catchments, there is no obvious relationship between the extent of weathering and climate types, which range from and to tropical. The most likely explanation for this observation is that the weathering profiles in many catchments are several Myr old, established during the much wetter Miocene period. The studied sediment compositions (excluding those from the Proterozoic catchments) are used to propose a new trace element normalisation termed MUQ (MUd from Queensland), which serves as an alternative to UCC proxies derived from sedimentary rocks. Copyright (C) 2005 Elsevier Ltd

Provenance of long-travelled dust determined with ultra-trace-element composition: A pilot study with samples from New Zealand glaciers

We report high-precision inductively coupled plasma mass spectrometric (ICP-MS) compositional data for 39 trace elements in a variety of dust deposits, trapped sediments and surface samples from New Zealand and Australia. Dusts collected from the surface of alpine glaciers in the Southern Alps, New Zealand, believed to have undergone long-distance atmospheric transport from Australia, are recognizable on account of their overabundances of Pb and Cu with respect to typical upper crustal values. Long-travelled dust from Australia therefore scavenges these and other metals (e.g. Zn, Sb and Cd) from the atmosphere during transport and deposition. Hence, due to anthropogenic pollution, long-travelled Australian dusts can be recognized by elevated metal contents. The relative abundance of 25 other elements that are not affected by atmospheric pollution, mineral sorting (Zr and Hf) and weathering/solubility (alkali and earth alkali elements) reflects the geochemistry of the dust source sediment. As a result, we are able to establish the provenance of dust using ultra-trace-element chemistry at regional scale. Comparison of long-travelled dust chemistry with potential Australian sources shows that fits of variable quality are obtained. We propose that the best fitting potential source chemistry most likely represents the major dust source area. A binary mixing model is used to demonstrate that admixture of small quantities of local dust provides an even better fitting dust chemistry for the long-travelled dusts. Copyright (c) 2005 John Wiley & Sons, Ltd.

Weathering geochronology by (U-Th)/He dating of goethite

Nine samples of supergene goethite (FeOOH) from Brazil and Australia were selected to rest the suitability of this mineral for (U-Th)/He dating. Measured He ages ranged from 61 to 8 Ma and were reproducible to better than a few percent despite very large Variations in [U] and [Th]. In all Samples with internal stratigraphy or independent age constraints, the He ages corroborated the expected relationship's. These data demonstrate that internally consistent He ages can be obtained on goethite. but do not prove quantitative 4 He retention. To assess possible diffusive He loss, stepped-heating experiments were performed on two goethite samples that were subjected to proton irradiation to produce a homogeneous distribution of spallogenic He-3. The He-3 release pattern indicates the presence of at least two diffusion domains, one with high helium retentivity and the other with very low retentivity at Earth surface conditions. The low retentivity domain, which accounts for similar to 5% of He-3, contains no natural He-4 and may represent poorly crystalline or intergranular material which has lost all radiogenic He-4 by diffusion in nature. Diffusive loss of He-3 from the high retentivity domain is independent of the macroscopic dimensions of the analyzed polycrystalline aggregate, so probably represents diffusion from individual micrometer-size goethite crystals. The He-2/He-3 evolution during the incremental heating experiments shows that the high retentivity domain has retained 90%-95% of its radiogenic helium. This degree of retentivity is in excellent agreement with that independently predicted from the helium diffusion coefficients extrapolated to Earth surface temperature and held for the appropriate duration. Considering both the high and low retentivity domains, these data indicate that one of the samples retained 90% of its radiogenic He-4 over 47.5 Ma and the other retained 86% over 12.3 Ma. Thus while diffusive-loss corrections to supergene goethite He ages are required. these initial results indicate that the corrections are not extremely large and can be rigorously quantified using the proton-irradiation He-4/He-3 method. Copyright (C) 2005 Elsevier Ltd.

Upper Devonian biostratigraphy of the Iberian Pyrite Belt, southwest Spain Part Two: Organic-walled microphytoplankton

Upper Devonian rocks of the Iberian Pyrite Belt (IPB) in southwest Spain, comprising the Phyllite-Quartzite Group (PQ) and the lower part of the overlying Volcano-Sedimentary Complex (VSC), contain a diversity of terrestrial and marine palynomorphs (miospores and organic-walled microphytoplankton, respectively), which constitute the basis of this biostratigraphically oriented research project. Part One of the report has previously detailed the miospore content of the constituent 117 palyniferous samples. In the present paper (i.e., the concluding Part Two), the organic-walled microphytoplankton (acritarchs and prasinophyte phycomata) are systematically described and illustrated, and their occurrence in the study material is fully documented. The acritarchs are represented by 23 species (including one species complex) allocated among 14 genera (one of which, Dupliciradiatum, is newly established), together with a very rare and novel category (informally termed Gen. nov. A). The following new acritarch species are formally instituted: Dupliciradiatum crassum (type species), D. tenue, Histopalla languida, and Winwaloeusia repagulata. Five genera allied with the prasinophycean algae are identified; these accommodate a total of 15 species of which two - Cymatiosphaera tenuimembrana and Maranhites multioculus - are formally proposed as new. In addition, representatives of the prasinophyte genera Leiosphaeridia and Tasmanites are recorded but are not discriminated at species level. The microphytoplankton suite is clearly consonant, from previously published occurrences in other regions, with a Late Devonian dating. However, most of the species are known to be relatively long ranging through (and in some cases beyond) that epoch and hence are not amenable to detailed biozonal subdivision of the IPB succession. Moreover, the distribution of the species therein tends to be erratic in comparison with the more consistently occurring miospores, possibly due to stress factors induced by fluctuating conditions in the IPBs Upper Devonian marine environment. By contrast, the land-derived (miospore) assemblages are readily applicable in a blostratigraphic context: they can be correlated precisely with the Devonian miospore biozonation scheme for Western Europe. In those terms, the sampled PQ strata are assignable to the Diducites versabilis-Grandispora cornuta (VCo) Biozone of late Famennian age; while the samples from the anoxic sequence at the base of the VSC belong to the Retispora lepidophyta-Verrucosisporites nitidus (LN) Biozone (latest Famennian = latest Devonian). The biochronostratigraphic data, in conjunction with the findings from earlier IPB studies, imply two appreciable palynostratigraphic breaks within the PQ. These are representative, respectively, of the lower Frasnian-middle Famennian interval and of part of the Strunian/upper Famennian. Speculation currently remains as to whether the inferred gaps are more apparent than real; i.e., whether one or both represent actual hiatuses in IPB sedimentation or are simply a manifestation of hitherto unsampled and/or non-palyniferous PQ strata.

Adverse feedback sequences in exploited marine systems: Are deliberate interruptive actions warranted?

Several mechanisms for self-enhancing feedback instabilities in marine ecosystems are identified and briefly elaborated. It appears that adverse phases of operation may be abruptly triggered by explosive breakouts in abundance of one or more previously suppressed populations. Moreover, an evident capacity of marine organisms to accomplish extensive geographic habitat expansions may expand and perpetuate a breakout event. This set of conceptual elements provides a framework for interpretation of a sequence of events that has occurred in the Northern Benguela Current Large Marine Ecosystem (off south-western Africa). This history can illustrate how multiple feedback loops might interact with one another in unanticipated and quite malignant ways, leading not only to collapse of customary resource stocks but also to degradation of the ecosystem to such an extent that disruption of customary goods and services may go beyond fisheries alone to adversely affect other major global ecosystem concerns (e.g. proliferations of jellyfish and other slimy, stingy, toxic and/or noxious organisms, perhaps even climate change itself, etc.). The wisdom of management interventions designed to interrupt an adverse mode of feedback operation is pondered. Research pathways are proposed that may lead to improved insights needed: (i) to avoid potential 'triggers' that might set adverse phases of feedback loop operation into motion; and (ii) to diagnose and properly evaluate plausible actions to reverse adverse phases of feedback operation that might already have been set in motion. These pathways include the drawing of inferences from available 'quasi-experiments' produced either by short-term climatic variation or inadvertently in the course of biased exploitation practices, and inter-regional applications of the comparative method of science.

Using continuous plankton recorder data

The continuous plankton recorder (CPR) survey is the largest multi-decadal plankton monitoring programme in the world. It was initiated in 1931 and by the end of 2004 had counted 207,619 samples and identified 437 phyto- and zoo-plankton taxa throughout the North Atlantic. CPR data are used extensively by the research community and in recent years have been used increasingly to underpin marine management. Here, we take a critical look at how best to use CPR data. We first describe the CPR itself, CPR sampling, and plankton counting procedures. We discuss the spatial and temporal biases in the Survey, summarise environmental data that have not previously been available, and describe the new data access policy. We supply information essential to using CPR data, including descriptions of each CPR taxonomic entity., the idiosyncrasies associated with counting many of the taxa, the logic behind taxonomic changes in the Survey, the semi-quantitative nature of CPR sampling, and recommendations on choosing the spatial and temporal scale of study. This forms the basis for a broader discussion on how to use CPR data for deriving ecologically meaningful indices based on size, functional groups and biomass that can be used to support research and management. This contribution should be useful for plankton ecologists, modellers and policy makers that actively use CPR data. (c) 2005 Elsevier Ltd. All rights reserved.