The issue of granite petrogenesis plays a key role in our overall understanding of the growth and differentiation of continents, as well as in our ability to unravel the tectonic histories of orogenic belts. Granites are ubiquitous magmatic products found in almost all tectonic settings: oceanic and continental rifts (i.e., plagiogranites - extreme basalt differentiates), active continental margins (e.g,. the granitic batholiths of central and southern Andes), continent-continent collision zones (e.g., the orogenic batholiths of the Himalayas, Western Anatolia), post-collisional settings (e.g., the Variscan provinces of Europe), complex within-plates settings (e.g., Limmo massif, Afar, Ethiopia). Furthermore, granitoids are characterized by considerable petrological and geochemical heterogeneity, as they can form from a vast array of sources: sediments (e.g., pelites, arkoses, psammites), metamorphic rocks (e.g., (mica)schists, gneisses, etc.), and igneous rocks (e.g. andesites, dacites, tonalites, etc.). Aside from fertile sources (i.e., protoliths), granite petrogenesis is dependent upon two critical parameters: temperature (to promote melting of the protoliths) and water availability - either as freely available aqueous solutions/vapors (e.g., water input in subduction zones); or water released via dehydration melting of hydrous minerals (e.g., micas, amphiboles). The presence of water in protoliths depresses the melting temperature of mineral components and provides the environment for redistribution of chemical components. Understanding the origins of granitic rocks presents unique challenges, given that in many of the tectonic settings where granites are encountered, it is clear that their modes of formation can involve a spectrum of igneous and metamorphic processes that are not readily accessible for examination, either through the study of modern environments or via analogy to "classical" localities. The petrogenesis and emplacement of granites in post-collisional tectonic settings is one of the thornier challenges, as these rocks appear to be derived via thermal and magmatic processes within highly deformed and compositionally diverse continental crust for which we lack a clear understanding. A number of unconventional and difficult-to-test mechanisms have been posited to drive crustal heating, melting, and subsequent pluton post-collisional emplacement. Although large volumes of granitic magmas have been emplaced in post-collisional settings, the complexities of the processes active in such settings make it challenging to put forward testable models that effectively combine available geochemical, petrologic, and geophysical data. Models for granite genesis away from plate margins (by means of crustal thickening, thermal blanketing, and internal heating from radioactive decay of 40K, 230Th, 235U, and 238U; delamination of the crustal lithosphere and juxtaposition of hot mantle melts at the base of the crust; underplating of mantle melts; or slab brake-off and upwelling of mantle melts) have been successfully applied in comparatively young orogenic regions, such as the Himalayas, the Carpathians, and Turkey. These models have proven challenging to employ in older orogenic belts, given their sometimes intricate tectonic and metamorphic histories, and the loss of pertinent evidence due to the effects of post-emplacement tectonic reworking, and often extensive alteration and erosion. A series of ancient but fresh, age-correlative granitic plutons are exposed in Alpine nappes on the flanks of the Carpathians Mountains in southwestern Romania. These granites, all mapped as intruding the Neoproterozoic basement of the Danubian tectonic terrane, were emplaced during the post-collisional stages of two world-scale orogenies: an older, Pan-African event (~600 Ma) and a younger, Variscan event (~330- 280 Ma). My dissertation is focused on the study of late Variscan post-collisional plutons and associated sub-volcanic dykes, as they are tremendous tools for understanding and quantifying the mantle-crust interaction in post-collisional environments and the overall evolution of the continental crust during the Variscan orogeny. Originally believed to be Proterozoic in age, zircon U/Pb dating showed that the plutons are much younger (Chapter 1 - Post-collisional Late Variscan magmatism in the Danubian domain (South Carpathians, Romania) documented by zircon U/Pb LA-ICP-MS) and correspond to the latest stages of the Variscan orogeny, as recorded elsewhere in the European Variscan provinces. The granitic plutons are relatively small and are generally concordant with the structures preserved by the country rocks. The extraordinary petrological and geochemical heterogeneities, even at pluton scale (Chapter 2 - Petrology and geochemistry of the Late Variscan post-collisional Furătura granitic pluton South. Carpathian Mts. (Romania)) argue against unique protoliths and simple evolutionary processes (e.g., closed-system fractional crystallization; anatexis). Trace elemental data for the Furătura pluton shows that the melts were formed in equilibrium with a garnet-amphibole restite, under pressure-temperature conditions deeper than the plagioclase stability field, implying that the melting took place at depths in excess of 40 km in the continental crust. Stable and radiogenic isotope data suggest that a protolith was of (possibly enriched) mantle affinities, and that the melts were subsequently contaminated in various degrees by deep crustal lithologies. In comparison, other post-collisional Variscan plutons from the Danubian domain (Chapter 4 - The role of the continental crust and lithospheric mantle in Variscan post-collisional magmatism - insights from Muntele Mic, Ogradena, Cherbelezu, Sfârdinu, and Culmea Cernei plutons (Romanian Southern Carpathians)) have trace elemental compositions that suggest they were formed at different levels in the crust, under P-T conditions corresponding to both garnet-amphibole and plagioclase stability fields. Some of the plutons lack mantle geochemical signatures and their isotopic compositions are indicative of substantial involvement of both lower- and upper-crustal rocks in their formation and subsequent evolution. On the other hand, plutons emplaced during the same time interval and most likely in close geographical proximity have trace elemental and isotopic compositions indicating strong input from previously enriched mantle components which experienced various degrees of assimilation fractionation-crystallization and/or assimilation of continental crust material during their evolution. This variability in both protoliths and processes responsible for the formation of the granites, coupled with the presence of mantle signatures in late-orogenic post-collisional melts are strong evidence to support delamination as means of providing both the mantle-derived input and energy required for generation of granitoids in the crust. The pronounced variation in petrological and chemical compositions of synchronous plutons suggests that delamination in the Danubian domain was not a single, large scale event that affected the entire crust, but rather a collection of disparate, spatially and chronologically limited event, that affected the Variscan crust during the latest stages of the orogeny. This hypothesis is further tested on a series of sub-volcanic dykes (the Motru Dyke Swarm) crosscutting the entire Danubian basement (Chapter 3 - Post-collisional magmatism associated with Variscan orogeny in the Danubian Domain (Romanian Southern Carpathians): the Motru Dyke Swarm). Initially, the emplacement age of these dykes was assumed as "pre-Silurian" but our mapping has showed that they intrude components of the Danubian domain that shared a documented common history not earlier than the Carboniferous. Furthermore, the dykes are in intrusive relationship with two of the Danubian Variscan plutons, thus arguing for an early Permian emplacement age. Geochemical data show extraordinary heterogeneities in the dykes' composition and record both mantle and crust involvement in their formation. The dykes were emplaced at much shallower depths in the crust, as compared with the granitic plutons. Still, their isotopic compositions clearly indicate that they sampled both lower- and upper-crustal compositions during their evolution. This means that after the crustal thickening episodes that define continent-continent collisions, during the latest stages of the Variscan orogeny, the crust became progressively thinner, as a way to compensate for its metastable state. Thinning of the crust is greatly favored by delamination of the lithosphere. A delamination event, which usually postdates the cessation of continental collision or prolonged crustal shortening, involves the geologically rapid foundering of negatively buoyant lithosphere comprised of mantle and (potentially) lower crust into underlying hotter and less dense asthenosphere. Such a process will remove the lithospheric mantle (and potentially segments of the lower crust) along pre-existing lineaments or mechanical flaws, and juxtapose hot upwelling asthenosphere against the base of the crust, leading to partial melting. Field, petrological, and geochemical data presented in my dissertation document pronounced variations in the overall composition of synchronous plutons and dykes, and further suggest that delamination in the Danubian domain was an active process. This bears great importance in our understanding of the evolution of the crust and argues that mantle-crust interactions are responsible for the generation of continental crust even in the latest stages of an orogen.

The Pieman River catchment has seen continuous mining of economic deposits of gold, silver, lead, copper, zinc and tin since the 1870’s. Tributaries of this river which receive mining effluent, either directly or from acid mine drainage (AMID), have total metal concentrations considerably above background levels and are of regulatory concern. The lower Pieman River is however classified as a State Reserve in which recreational fishing and tourism are the major activities. It is therefore important that water entering the lower Pieman River from upstream hydroelectric impoundments is of high quality. Metals in natural waters exist in a variety of dissolved, colloidal and particulate forms. The bioavailability and hence toxicity of heavy metal pollutants is very dependant on their physico form. Knowledge of the speciation of a metal in natural aquatic environments is therefore necessary for understanding its geochemical behaviour and biological availability. Complexation of metal ions by natural ligands in aquatic systems is believed to play a significant role in controlling their chemical speciation. This study has investigated temporal and spatial variation in complexation of metal ions in the Pieman River. The influence of pH, temperature, organic matter, salinity, ionic strength and time has been investigated in a series of field studies and in laboratory-based experiments which simulated natural and anthropogenic disturbances. Labile metals were measured using two techniques in various freshwater and estuarine environments. Diffusive gradients in thin-films (DGT) allowed in situ measurement of solution speciation whilst differential pulse anodic stripping voltammetry (DPASV) was used to measure labile metal species in water samples collected from the catchment. Organic complexation was found to be a significant regulating mechanism for copper speciation and the copper-binding ligand concentration usually exceeded the total copper concentration in the river water. Complexation was highly dependent on pH and at the river-seawater interface was also regulated by salinity, probably as a result of competitive complexation by major ions in seawater (eg. Ca 2+ ions). Zinc complexation was also evident, however total zinc concentrations in the water column often far exceeded the potential binding capacity of available ligands. In addition to organic complexation, Zn speciation may also be associated with adsorption by flocculated or resuspended colloidal Mn and/or Fe oxyhydroxides. Metal ion complexation and hence speciation was found to be highly variable within the Pieman River catchment. This presents major difficulties for environmental managers, as it is therefore not possible to make catchment-wide assumptions about the bioavailability of these metals. These results emphasise the importance of site-specific sampling protocols and speciation testing, ideally incorporating continuous, in situ monitoring.

Provenance in the lower Belt-Purcell Supergroup is constrained based on geochemical systematics and chemical monazite ages of argillites and sandstones. Rare earth element (REE), Cr-Ni, and Th/Sc-Sc systematics is equivalent for both facies and consistent with a dominantly post-Archean source area. Detrital monazite chemical ages restrict major provenance for the Appekunny and Grinnell sandstones and argillites to Paleoproterozoic terranes at ~1800-1600 Ma, minor contributions at ~1600-1500 Ma, and marginal contributions from Archean terranes at ~2600, likely in Laurentia. Similar detrital age spectra for monazites of argillites and sandstones of the Appekunny Formation are consistent with a common provenance for the two facies.</p> <p>The Belt-Purcell sequence records three major diagenetic stages displayed in argillites and sandstones: (1) K-addition and rare earth element post-Archean upper continental crust (PA-UCC)-like pattern; (2) a stage characterized by heavy REE enrichment relative to light REE and HFSE fractionation, and U and Ce mobility; and (3) local dolomitization with REE and high field strenght elements (HFSE) mobility. REE and HFSE mobility are interpreted as the result of oxidized alkaline brines developed by dissolution of evaporites. Monazites from the Appekunny and Grinnell formations differ compositionally and texturally in two groups. Rounded or inclusions with ages >~1400 Ma, interpreted as detrital, have higher Th2O, Y2O3 and lower LREE/HREE contents than euhedral individual monazite grains with chemical ages <~1400 Ma that posses opposed compositional characteristics, and viewed as diagenetic. Monazites that span <~1400 to 300 Ma could be the result of basinal brine activity during stages (2) and (3). </p> <p>Chemical index of alteration (CIA) for argillites and sandstones, corrected for a diagenetic K-addition average 73 and 66 respectively. These results, coupled with correlation of CIA with Eu/Eu*, low K/Cs ratios, and low Sr, Ca, and Na relative to PA-UCC, could be interpreted as the result of an moderate weathered provenance in a hot, wet climate being drained by a large-scale river system. Presence of minor pristine feldspars lowers the CIA values, and may signify minor contributions from proximal source with short-river transport under the arid to semi-arid climate in the depositional setting. Moderate to intense weathering of the larger provenance may be associated with elevated levels of atmospheric CO2 degassed from a mantle plume implicated in the rifting of the supercontinent Columbia at ~1500 Ma.

Range expansion events of the Humboldt squid reveal our inadequate understanding of populations of this species. Despite recent hatching, reproductive, tagging, genetic and dietary studies of Dosidicus gigas, much speculation remains concerning geographic migration, stock assessment and habitat preferences. This study provides evidence that statolith trace elemental variations can be useful in distinguishing among geographic populations. Specimens were collected from the Galapagos Islands, southern California, and Washington State. A dissection method was recorded and published. By using laser ablation methods, discrete measurements of 10 elements were collected at 6 to 7 ablation sites covering embryonic, paralarval, juvenile and adult stages. Analysis of Variance revealed important ontogenic elemental variations among ablation locations. Multivariate Analysis of Variance, ordination techniques and discriminant function analysis with permutation testing were all utilized to compare and characterize the variations found in elemental concentrations. Significant ontogenic variations were found for 8 out of the 10 focus elements; this is the first report for 5 of these elements for this species. The geographic populations were effectively classified as distinct group for the first time using these methods. Elemental fingerprint signatures were found to be significantly different at multiple ontogenic growth regions of the statolith. Seattle and California paralarvae exhibited similar elemental signatures despite significant differences in those found in the embryonic core and juvenile regions of the statolith. These methods are a useful tool in providing stock assessment and can be improved for use in future population dynamics models.

The Saint-Urbain and Big Island rutile-bearing ilmenite Fe-Ti oxide deposits are located in the composite 450 km² Saint-Urbain anorthosite (1055-1046 Ma, U-Pb zircon) and in the Lac Allard intrusion (1057-1062 Ma, U-Pb zircon) of the 11,000 km² Havre-Saint Pierre anorthosite suite, respectively, in the Grenville Province of Eastern Canada. Slow cooling rates of 3-4°C/m.y. are estimated for both anorthosites, based on combined U-Pb zircon/rutile/apatite and ⁴⁰Ar/³⁹ Ar biotite/plagioclase geochronology, and resulted from emplacement during the active Ottawan Orogeny. Slow cooling facilitated (1) diffusion of Zr from ilmenite and rutile, producing thin (10-100 microns) zircon rims on these minerals, and (2) formation of sapphirine via sub-so lidus reactions of the type: spinel + orthopyroxene + rutile ± corundum → sapphirine + ilmenite. New chemical and analytical methods were developed to determine the trace element concentrations and Hf isotopic compositions of Ti-based oxides. Rutile is a magmatic phase in the deposits with minimum crystallization temperatures of 781°C to 1016°C, calculated by Zr-in rutile thermometry. Ilmenite present in rutile-free samples has higher Xhem (hematite proportion in ilmenite), higher high field strength element concentrations (Xhem = 30-17; Nb = 16.1-30.5 ppm; Ta 1.28-1.70 ppm), and crystallized at higher temperatures than ilmenite with more fractionated compositions (Xhem = 21-11; Nb = 1.36-3.11 ppm; Ta = <0.18 ppm) from rutile-bearing rocks. The oxide deposits formed by density segregation and accumulation at the bottom of magma reservoirs, in conditions closed to oxygen, from magmas enriched in Fe and Ti. The initial ¹⁷⁶Hf/¹⁷⁷ Hf of rutile and ilmenite (Saint Urbain [SU] = 0.28219-0.28227, Big Island [BI] = 0.28218-0.28222), and the initial Pb isotopic ratios (e.g.²⁰⁶Pb/²⁰⁴ Pb: SU = 17.134-17.164, BI = 17.012-17.036) and ⁸⁷Sr/⁸⁶ Sr (SU = 0.70399-0.70532, BI = 0.70412-0.70427) of plagioclase from the deposits overlap with the initial isotopic ratios of ilmenite and plagioclase from each host anorthosite, which indicates that they have common parent magmas and sources. The parent magmas were derived from a relatively depleted mantle reservoir that appears to be the primary source of all Grenvillian anorthosite massifs and existed for --600 m.y. along the margin of Laurentia during the Proterozoic.

Provenance in the lower Belt-Purcell Supergroup is constrained based on geochemical systematics and chemical monazite ages of argillites and sandstones. Rare earth element (REE), Cr-Ni, and Th/Sc-Sc systematics is equivalent for both facies and consistent with a dominantly post-Archean source area. Detrital monazite chemical ages restrict major provenance for the Appekunny and Grinnell sandstones and argillites to Paleoproterozoic terranes at ~1800-1600 Ma, minor contributions at ~1600-1500 Ma, and marginal contributions from Archean terranes at ~2600, likely in Laurentia. Similar detrital age spectra for monazites of argillites and sandstones of the Appekunny Formation are consistent with a common provenance for the two facies.</p> <p>The Belt-Purcell sequence records three major diagenetic stages displayed in argillites and sandstones: (1) K-addition and rare earth element post-Archean upper continental crust (PA-UCC)-like pattern; (2) a stage characterized by heavy REE enrichment relative to light REE and HFSE fractionation, and U and Ce mobility; and (3) local dolomitization with REE and high field strenght elements (HFSE) mobility. REE and HFSE mobility are interpreted as the result of oxidized alkaline brines developed by dissolution of evaporites. Monazites from the Appekunny and Grinnell formations differ compositionally and texturally in two groups. Rounded or inclusions with ages >~1400 Ma, interpreted as detrital, have higher Th2O, Y2O3 and lower LREE/HREE contents than euhedral individual monazite grains with chemical ages <~1400 Ma that posses opposed compositional characteristics, and viewed as diagenetic. Monazites that span <~1400 to 300 Ma could be the result of basinal brine activity during stages (2) and (3). </p> <p>Chemical index of alteration (CIA) for argillites and sandstones, corrected for a diagenetic K-addition average 73 and 66 respectively. These results, coupled with correlation of CIA with Eu/Eu*, low K/Cs ratios, and low Sr, Ca, and Na relative to PA-UCC, could be interpreted as the result of an moderate weathered provenance in a hot, wet climate being drained by a large-scale river system. Presence of minor pristine feldspars lowers the CIA values, and may signify minor contributions from proximal source with short-river transport under the arid to semi-arid climate in the depositional setting. Moderate to intense weathering of the larger provenance may be associated with elevated levels of atmospheric CO2 degassed from a mantle plume implicated in the rifting of the supercontinent Columbia at ~1500 Ma.

Water samples were collected from coastal region off southwestern Taiwan during two cruises in different seasons (October, 2008 and March, 2010). In order to provide information for trace elements in this region, this study investigated the distribution and partitioning of dissolved trace elements (Cd, Cu, Ni, Zn), and to relate the influences of complicated hydrological conditions to trace element distributions. Fractionation of dissolved trace elements was applied by a one-step preconcentration technique which uses cationic and anionic exchange columns. Trace element fractions were separated to operationally defined reactive (Chelex-labile), organically complexed (anionic-organic), and stable (inert) species. Distributions of trace elements from near-shore surface waters off southwestern Taiwan were mainly affected by temporally variable terrigenous inputs and hydrological conditions. The most significant sources of trace elements were from the Gao-Ping, Er-Ren, and Tseng-Wen Rivers. Some near-shore vertical profiles of trace elements and nutrients showed abnormal distributions that could be attributed to complicated currents in this region. Trace elements in waters at offshore stations in this study showed nutrient-type distributions, and that is similar to other open ocean vertical profiles, except for the upper layers, where terrestrial influences were pronounced in this study. The major proportions of trace elements determined in this study were of the Chelex-labile fractions, indicating that they were reactive and bioavailable. There is a small part of inert fraction, and the proportions are different between inshore and offshore waters, with pronounced inert fractions in near-shore waters.

Thesis (Ph. D.)--Rutgers University, 2008. / "Graduate Program in Environmental Sciences." Includes bibliographical references.

Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2004. / Includes bibliographical references. Also available in electronic version. Access restricted to campus users.

Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (leaves 82-95).