Zircon U-Pb and Hf-O analysis of porphyries from the Duolong porphyry Cu-Au deposit in the Bangongco copper belt, central Tibet

The Duolong porphyry Cu-Au deposit (5.4 Mt at 0.72% Cu, 41 t at 0.23 g/t Au), which is related to the granodiorite porphyry and the quartz-diorite porphyry from the Bangongco copper belt in central Tibet, formed in a continental arc setting. Here, we present the zircon U-Pb ages, geochemical whole-rock, Sr-Nd whole-rock and zircon in-situ Hf-O isotopic data for the Duolong porphyries. Secondary ion mass spectrometry (SIMS) zircon U-Pb analyses for six samples yielded consistent ages of ~118 Ma, indicating a Cretaceous formation age. The Duolong porphyries (SiO2 of 58.81-68.81 wt.%, K2O of 2.90-5.17 wt.%) belong to the high-K calc-alkaline series. They show light rare earth element (LREE)-enriched distribution patterns with (La/Yb)N = 6.1-11.7, enrichment in large ion lithophile elements (e.g., Cs, Rb, and Ba) and depletion of high field strength elements (e.g., Nb), with negative Ti anomalies. All zircons from the Duolong porphyries share relatively similar Hf-O isotopic compositions (d18O=5.88-7.27 per mil; eHf(t)=3.6-7.3), indicating that they crystallized from a series of cogenetic melts with various degrees of fractional crystallization. This, along with the general absence of older inherited zircons, rules out significant crustal contamination during zircon growth. The zircons are mostly enriched in d18O relative to mantle values, indicating the involvement of an 18O-enriched crustal source in the generation of the Duolong porphyries. Together with the presence of syn-mineralization basaltic andesite, the mixing between silicic melts derived from the lower crust and evolved H2O-rich mafic melts derived from the metsomatizied mantle wedge, followed by subsequent fractional crystallization (FC) and minor crustal contamination in the shallow crust, could well explain the petrogenesis of the Duolong porphyries. Significantly, the hybrid melts possibly inherited the arc magma characteristics of abundant F, Cl, Cu, and Au elements and high oxidation state, which contributed to the formation of the Duolong porphyry Cu-Au deposit.

Element and isotope compostion of basalts and sediments from the Japan Sea

Ocean Drilling Program Legs 127 and 128 in the Yamato Basin of the Japan Sea, a Miocene-age back-arc basin in the western Pacific Ocean, recovered incompatible-element-depleted and enriched tholeiitic dolerites and basalts from the basin floor, which provide evidence of a significant sedimentary component in their mantle source. Isotopically, the volcanic rocks cover a wide range of compositions (e.g., 87Sr/86Sr = 0.70369 - 0.70503, 206Pb/204Pb = 17.65 - 18.36) and define a mixing trend between a depleted mantle (DM) component and an enriched component with the composition of EM II. At Site 797, the combined isotope and trace element systematics support a model of two component mixing between depleted, MORB-like mantle and Pacific pelagic sediments. A best estimate of the composition of the sedimentary component has been determined by analyzing samples of differing lithology from DSDP Sites 579 and 581 in the western Pacific, east of the Japan arc. The sediments have large depletions in the high field strength elements and are relatively enriched in the large-ion-lithophile elements, including Pb. These characteristics are mirrored, with reduced amplitudes, in Japan Sea enriched tholeiites and northeast Japan arc lavas, which strengthens the link between source enrichment and subducted sediments. However, Site 579/581 sediments have higher LILE/REE and lower HFSE/REE than the enriched component inferred fiom mixing trends at Site 797. Sub-arc devolatilization of the sediments is a process that will lower LILE/REE and raise HFSE/REE in the residual sediment, and thus this residual sediment may serve as the enriched component in the back-arc basalt source. Samples from other potential sources of an enriched, EM II-like component beneath Japan, such as the subcontinental lithosphere or crust, have isotopic compositions which overlap those of the Japan Sea tholeiites and are not "enriched" enough to be the EM II end-member.

Table A1 LA-ICP-MS zircon U-Pb data of Laoniushan granitoids

The NWW-striking Qinling Orogen formed in the Triassic by collision between the North China and Yangtze Cratons. Triassic granitoid intrusions, mostly middle- to high-K, calc-alkaline in composition, are widespread in this orogen, but contemporaneous intrusions are rare in the southern margin of the North China Craton, an area commonly considered as the hinterland belt of the orogen. In this paper, we report zircon U-Pb ages, elemental geochemistry, and Sr-Nd-Hf isotope data for the Laoniushan granitoid complex that was emplaced in the southern margin of the North China Craton. Zircon U-Pb dating shows that the complex was emplaced in the late Triassic (228±1 to 215±4 Ma), indicating that it is part of the post-collisional magmatism in the Qinling Orogen. The complex consists of, from early to late, biotite monzogranite, quartz diorite, quartz monzonite, and hornblende monzonite, which have a wide compositional range, e.g., SiO2=55.9-70.6 wt%, K2O+Na2O=6.6-10.2 wt%, and Mg# of 24 to 54. Rocks of the biotite monzogranite have high Al2O3(15.5-17.4 wt%), Sr(396-1398 ppm) and Ba(1284-3993 ppm) contents and La/Yb(mostly 14-30) and Sr/Y(mostly 40-97) ratios, but low Yb(mostly 1.3-1.6 ppm) and Y(mostly14-19 ppm) contents, features typical of adakite. The quartz monzonite, hornblende monzonite and quartz diorite have a shoshonitic affinity, with K2O up to 5.58 wt% and K2O/Na2O ratios averaging 1.4. The rocks are characterized by strong LREE/HREE fractionation in chondrite-normalized REE pattern, without obvious Eu anomalies, and show enrichment in large ion lithophile elements but depletion in high field strength elements (Nb, Ta, Ti). The biotite monzogranite (228 Ma) has initial 87Sr/86Sr ratios of 0.7061 to 0.7067, eNd(t) values of -9.2 to -12.6, and ?Hf(t) values of -9.0 to -15.1; whereas the shoshonitic granitoids (mainly 217-215 Ma) have similar initial 87Sr/86Sr ratios (0.7065 to 0.7075) but more radiogenic eNd(t) (-12.4 to -17.0) and eHf(t) (-14.1 to -17.0). The Sr-Nd-Hf isotope data indicate that the rocks were likely generated by partial melting of an ancient lower continental crust with heterogeneous compositions, as partly confirmed by the widespread presence of the early Paleoproterozoic inherited zircons. Mafic microgranular enclaves (MMEs), characterized by fine-grained igneous textures and an abundance of acicular apatites, are common in the Laoniushan complex. Compared with the host rocks, they have lower SiO2 (48.6-53.7 wt.%) and higher Mg# (51-56), Cr (122-393 ppm), and Ni (24-79 ppm), but equivalent Sr-Nd isotope compositions, indicating that the MMEs likely originated from an ancient enriched lithospheric mantle. The abundance of MMEs in the granitoid intrusions suggests that magma mixing plays an important role in the generation of the Laoniushan complex. Collectively, it is suggested that the Laoniushan complex was a product of post-collisional magmatism related to lithospheric extension following slab break-off. Formation of the adakitic and shoshonitic intrusions in the Laoniushan complex indicates that the Qinling Orogen had evolved into a post-collisional setting by about 230-210 Ma.

Rock magnetic properties and radiocarbon dates of samples obtained on Ile de Possession, South Indian Ocean

A 6200 year old peat sequence, cored in a volcanic crater on the sub-Antarctic Ile de la Possession (Iles Crozet), has been investigated, based on a multi-proxy approach. The methods applied are macrobotanical (mosses, seeds and fruits) and diatom analyses, complemented by geochemical (Rock-Eval6) and rock magnetic measurements. The chronology of the core is based on 5 radiocarbon dates. When combining all the proxy data the following changes could be inferred. From the onset of the peat formation (6200 cal yr BP) until ca. 5550 cal yr BP, biological production was high and climatic conditions must have been relatively warm. At ca. 5550 cal yr BP a shift to low biological production occurred, lasting until ca. 4600 cal yr BP. During this period the organic matter is well preserved, pointing to a cold and/or wet environment. At ca. 4600 cal yr BP, biological production increased again. From ca. 4600 cal yr BP until ca. 4100 cal yr BP a 'hollow and hummock' micro topography developed at the peat surface, resulting in the presence of a mixture of wetter and drier species in the macrobotanical record. After ca. 4100 cal yr BP, the wet species disappear and a generally drier, acidic bog came into existence. A major shift in all the proxy data is observed at ca. 2800 cal yr BP, pointing to wetter and especially windier climatic conditions on the island probably caused by an intensification and/or latitudinal shift of the southern westerly belt. Caused by a stronger wind regime, erosion of the peat surface occurred at that time and a lake was formed in the peat deposits of the crater, which is still present today.

Chemistry of altered basaltic glass shards and zeolites of volcaniclastic sediments from ODP Hole 157-953C

Trace element concentrations of altered basaltic glass shards (layer silicates) and zeolites in volcaniclastic sediments drilled in the volcanic apron northeast of Gran Canaria during Ocean Drilling Program (ODP) leg 157 document variable element mobilities during low-temperature alteration processes in a marine environment. Clay minerals (saponite, montmorillonite, smectite) replacing volcanic glass particles are enriched in transition metals and rare earth elements (REE). The degree of retention of REE within the alteration products of the basaltic glass is correlated with the field strength of the cations. The high field-strength elements are preferentially retained or enriched in the alteration products by sorption through clay minerals. Most trace elements are enriched in a boundary layer close to the interface mineral-altered glass. This boundary layer has a key function for the physico-chemical conditions of the subsequent alteration process by providing a large reactive surface and by lowering the fluid permeability. The release of most elements is buffered by incorporation into secondary precipitates (sodium-rich zeolites, phillipsite, Fe- and Mn-oxides) as shown by calculated distribution coefficients between altered glasses and authigenic minerals. Chemical fluxes change from an open to a closed system behavior during prograde low-temperature alteration of volcaniclastic sediments with no significant trace metal flux from the sediment to the water column.

Whole-rock geochemical analyses of serpentinized harzburgites from ODP Site 209-1270

Small-scale shear zones are present in drillcore samples of abyssal peridotites from the Mid-Atlantic ridge at 15°20'N (Ocean Drilling Program Leg 209). The shear zones act as pathways for both evolved melts and hydrothermal fluids. We examined serpentinites directly adjacent to such zones to evaluate chemical changes resulting from melt-rock and fluid-rock interaction and their influence on the mineralogy. Compared to fresh harzburgite and melt-unaffected serpentinites, serpentinites adjacent to melt-bearing veins show a marked enrichment in rare earth elements (REE), strontium and high field strength elements (HFSE) zirconium and niobium. From comparison with published chemical data of variably serpentinized and melt-unaffected harzburgites, one possible interpretation is that interaction with the adjacent melt veins caused the enrichment in HFSE, whereas the REE contents might also be enriched due to hydrothermal processes. Enrichment in alumina during serpentinization is corroborated by reaction path models for interaction of seawater with harzburgite-plagiogranite mixtures. These models explain both increased amounts of alumina in the serpentinizing fluid for increasing amounts of plagiogranitic material mixed with harzburgite, and the absence of brucite from the secondary mineralogy due to elevated silica activity. By destabilizing brucite, nearby melt veins might fundamentally influence the low-temperature alteration behaviour of serpentinites. Although observations and model results are in general agreement, due to absence of any unaltered protolith a quantification of element transport during serpentinization is not straightforward.

(Table 1) Rock magnetic parameters of core samples obtained from Morne Rouge, Ile de Possession

The magnetic high field susceptibility chi(hifi) indicates the presence of mafic paramagnetic minerals in the scoriae and points to an absence of clay minerals, and in turn of pedogenic processes, in the peat samples. Due to their volcanic origin, scoriae contain much more ferrimagnetic minerals than peat with is indicated by their enhanced saturation remanence Mrs.

Petrology, geochemistry and K-Ar Age determination of De Gerlache Seamount basalts

The De Gerlache Seamounts are two topographic highs in the Bellingshausen Sea, southeastern Pacific. Petrological and geochemical studies together with K-Ar age determinations were carried out on four dredged basalt samples collected during a RV Polarstern expedition (ANT-XII/4) in 1995. Minor and trace element composition suggest alkaline basalt compositions. Compared to alkaline basalts of adjacent West Antarctica (the Jones Mountains) and of Peter I Island, the samples have lower mg-numbers, lower Ni and Cr contents and lower high field-strength elements (HFSE)/Nb and large-ion lithophile elements (LILE)/HFSE ratios. Three of the four samples have low K, Rb, and Cs concentrations relative to alkaline basalts. The K-depletion and other elemental concentrations may be explained by 1.1% melting of amphibole bearing mantle material. Additionally, low Rb and Ba values suggest low concentrations of these elements in the mantle source. K-Ar age determinations yield Miocene ages (20-23 Ma) that are similar in age to other alkaline basalts of West Antarctica (Thurston Island, the Jones Mountains, Antarctic Peninsula) and the suggested timing of onset of Peter I Island volcanism (~10-20 Ma). The occurrence of the DGS and Peter I Island volcanism along an older but reactivated tectonic lineation suggests that the extrusions exploited a zone of pre-existing lithospheric weakness. The alkaline nature and age of the DGS basalts support the assumption of plume activity in the Bellingshausen Sea.

(Table 1) Sedimentary thicknesses, lithologies, ages, and interpreted paleowater depths for ODP Sites 135-840 and 135-841

The sedimentary succession drilled at Sites 840 and 841 on the Tonga forearc allows the sedimentary evolution of the active margin to be reconstructed since shortly after the initiation of subduction during the mid Eocene. Sedimentation has been dominated by submarine fan deposits, principally volcaniclastic turbidites and mass-flows derived from the volcanic arc. Volcaniclastic sedimentation occurred against a background of pelagic nannofossil sedimentation. A number of upward-fining cycles are recognized and are correlated to regional tectonic events, such as the rifting of the Lau Basin at 5.6 Ma. Episodes of sedimentation dating from 16.0 and 10.0 Ma also correlate well with major falls in eustatic sea level and may be at least partially caused by the resulting enhanced erosion of the arc edifice. The early stages of rifting of the Lau Basin are marked by the formation of a brief hiatus at Site 840 (Horizon A), probably a result of the uplift of the Tonga Platform. Controversy exists as to the degree and timing of the uplift of Site 840 before Lau Basin rifting, with estimates ranging from 2500 to 300 m. Structural information favors a lower value. Breakup of the Tonga Arc during rifting resulted in deposition of dacite-dominated, volcaniclastic mass flows, probably reflecting a maximum in arc volcanism at this time. A pelagic interval at Site 840 suggests that no volcanic arc was present adjacent to the Tonga Platform from 5.0 to 3.0 Ma. This represents the time between separation of the Lau Ridge from the Tonga Platform and the start of activity on the Tofua Arc at 3.0 Ma. The sedimentary successions at both sites provide a record of the arc volcanism despite the reworked nature of the deposits. Probe analyses of volcanic glass grains from Site 840 indicate a consistent low-K tholeiite chemistry from 7.0 Ma to the present, possibly reflecting sediment sourcing from a single volcanic center over long periods of time. Trace and rare-earth-element (REE) analyses of basaltic glass grains indicate that thinning of the arc lithosphere had begun by 7.0 Ma and was the principle cause of a progressive depletion of the high-field-strength (HFSE), REE, and large-ion-lithophile (LILE) elements within the arc magmas before rifting. Magmatic underplating of the Tofua Arc has reversed this trend since that time. Increasing fluid flux from the subducting slab since basin rifting has caused a progressive enrichment in LILEs. Subduction erosion of the underside of the forearc lithosphere has caused continuous subsidence and tilting toward the trench since 37.0 Ma. Enhanced subsidence occurred during rifting of the South Fiji and Lau basins. Collision of the Louisville Ridge with the trench has caused no change in the nature of the sedimentation, but it may have been responsible for up to 300 m of uplift at Site 840.

Natural remanent magnetization (NRM) from ODP Site 1263 covering magnetochron C20r and C21n and high-resolution bulk carbon isotope (d13C) records from Sites 702 and 1263

To explore cause and consequences of past climate change, very accurate age models such as those provided by the astronomical timescale (ATS) are needed. Beyond 40 million years the accuracy of the ATS critically depends on the correctness of orbital models and radioisotopic dating techniques. Discrepancies in the age dating of sedimentary successions and the lack of suitable records spanning the middle Eocene have prevented development of a continuous astronomically calibrated geological timescale for the entire Cenozoic Era. We now solve this problem by constructing an independent astrochronological stratigraphy based on Earth's stable 405 kyr eccentricity cycle between 41 and 48 million years ago (Ma) with new data from deep-sea sedimentary sequences in the South Atlantic Ocean. This new link completes the Paleogene astronomical timescale and confirms the intercalibration of radioisotopic and astronomical dating methods back through the Paleocene-Eocene Thermal Maximum (PETM, 55.930 Ma) and the Cretaceous-Paleogene boundary (66.022 Ma). Coupling of the Paleogene 405 kyr cyclostratigraphic frameworks across the middle Eocene further paves the way for extending the ATS into the Mesozoic.

Habitat map of Danajon Bank, Philippines, derived from a high-spatial-resolution multi-spectral satellite image and georeferenced point intercept transect and spot-check survey field data, using an object-based image classification method

A mosaic of two WorldView-2 high resolution multispectral images (Acquisition dates: October 2010 and April 2012), in conjunction with field survey data, was used to create a habitat map of the Danajon Bank, Philippines (10°15'0'' N, 124°08'0'' E) using an object-based approach. To create the habitat map, we conducted benthic cover (seafloor) field surveys using two methods. Firstly, we undertook georeferenced point intercept transects (English et al., 1997). For ten sites we recorded habitat cover types at 1 m intervals on 10 m long transects (n= 2,070 points). Second, we conducted geo-referenced spot check surveys, by placing a viewing bucket in the water to estimate the percent cover benthic cover types (n = 2,357 points). Survey locations were chosen to cover a diverse and representative subset of habitats found in the Danajon Bank. The combination of methods was a compromise between the higher accuracy of point intercept transects and the larger sample area achievable through spot check surveys (Roelfsema and Phinn, 2008, doi:10.1117/12.804806). Object-based image analysis, using the field data as calibration data, was used to classify the image mosaic at each of the reef, geomorphic and benthic community levels. The benthic community level segregated the image into a total of 17 pure and mixed benthic classes.