Composition of sedimentary rocks from the Burun-Tas Formation, Bol'shoi Lyakhov Island (New Siberian Islands)

Graywackes and shales of the Bol'shoi Lyakhov Island originally attributed to Mesozoic were subsequently considered based on microfossils as Late Proterozoic in age. At present, these sediments in the greater part of the island are dated back to Permian based on palynological assemblages. In the examined area of the island, this siliciclastic complex is intensely deformed and tectonically juxtaposed with blocks of oceanic and island-arc rocks exhumed along the South Anyui suture. The complex is largely composed of turbidites with members displaying hummocky cross-stratification. Studied mineral and geochemical charac¬teristics of the rocks defined three provenances of clastic material: volcanic island arc, sedimentary cover and/or basement of an ancient platform, and exotic blocks of oceanic and island-arc rocks such as serpentinites and amphibolites. All rock associations represent elements of an orogenic structure that originated by collision of the New Siberian continental block with the Anyui-Svyatoi Nos island arc. Flyschoid sediments accumu¬lated in a foredeep in front of the latter structure in the course of collision. Late Jurassic volcanics belonging to the Anyui-Svyatoi Nos island arc determine the lower age limit of syncollision siliciclastic rocks. Presence of Late Jurassic zircons in sandstones of the flyschoid sequence in the Bol'shoi Lyakhov Island is confirmed by fission-track dating. The upper age limit is determined by Aptian-Albian postcollision granites and diorites intruding the siliciclastic complex. Consequently, the flyschoid sequence is within stratigraphic range from the terminal Late Jurassic to Neocomian. It appears that Permian age of sediments suggested earlier is based on redeposited organic remains. The same Late Jurassic-Neocomian age and lithology are characteristic of fossiliferous siliciclastic sequences of the Stolbovoi and Malyi Lyakhov islands, the New Siberian Archipelago, and of graywackes in the South Anyui area in the Chukchi Peninsula. All these sediments accumulated in a spacious foredeep that formed in the course the late Cimmerian orogeny along the southern margin of the Arctic conti¬nental block.

Geochemistry of basalts from the Caribbean Large Igneous Province

Oceanic flood basalts are poorly understood, short-term expressions of highly increased heat flux and mass flow within the convecting mantle. The uniqueness of the Caribbean Large Igneous Province (CLIP, 92-74 Ma) with respect to other Cretaceous oceanic plateaus is its extensive sub-aerial exposures, providing an excellent basis to investigate the temporal and compositional relationships within a starting plume head. We present major element, trace element and initial Sr-Nd-Pb isotope composition of 40 extrusive rocks from the Caribbean Plateau, including onland sections in Costa Rica, Colombia and Curaçao as well as DSDP Sites in the Central Caribbean. Even though the lavas were erupted over an area of ~3*10**6 km**2, the majority have strikingly uniform incompatible element patterns (La/Yb=0.96+/-0.16, n=64 out of 79 samples, 2sigma) and initial Nd-Pb isotopic compositions (e.g. 143Nd/144Ndin=0.51291+/-3, epsilon-Nd i=7.3+/-0.6, 206Pb/204Pbin=18.86+/-0.12, n=54 out of 66, 2sigma). Lavas with endmember compositions have only been sampled at the DSDP Sites, Gorgona Island (Colombia) and the 65-60 Ma accreted Quepos and Osa igneous complexes (Costa Rica) of the subsequent hotspot track. Despite the relatively uniform composition of most lavas, linear correlations exist between isotope ratios and between isotope and highly incompatible trace element ratios. The Sr-Nd-Pb isotope and trace element signatures of the chemically enriched lavas are compatible with derivation from recycled oceanic crust, while the depleted lavas are derived from a highly residual source. This source could represent either oceanic lithospheric mantle left after ocean crust formation or gabbros with interlayered ultramafic cumulates of the lower oceanic crust. High 3He/4He in olivines of enriched picrites at Quepos are ~12 times higher than the atmospheric ratio suggesting that the enriched component may have once resided in the lower mantle. Evaluation of the Sm-Nd and U-Pb isotope systematics on isochron diagrams suggests that the age of separation of enriched and depleted components from the depleted MORB source mantle could have been <=500 Ma before CLIP formation and interpreted to reflect the recycling time of the CLIP source. Mantle plume heads may provide a mechanism for transporting large volumes of possibly young recycled oceanic lithosphere residing in the lower mantle back into the shallow MORB source mantle.

Desenvolvimento de método para determinação de espécies de mercúrio empregando MSPD e GC-MS

Neste trabalho é proposto pela primeira vez, o desenvolvimento e validação de um método analítico baseado no emprego da dispersão da matriz em fase sólida (MSPD) modificada, para extração das espécies CH3Hg+ e Hg2+ em amostras de peixe e determinação por cromatografia em fase gasosa acoplada à espectrometria de massas (GC-MS). O método de extração utilizando a MSPD combina o rompimento da estrutura física da amostra, através da maceração e do uso de SiO2 como suporte sólido, com o método da extração ácida, utilizando uma solução de HCl 4,2 mol L-1 e NaCl 0,5 mol L-1. Para otimização da MSPD, foram avaliados parâmetros como massa de amostra, massa de suporte sólido, concentração de HCl, concentração de NaCl, tipo de suporte sólido e o tempo de agitação, com auxílio da metodologia de superfície de resposta. Além disso, a etapa de derivatização e a separação cromatográfica também foram otimizadas na determinação de CH3Hg+ e Hg2+ por GC-MS. O método mostrouse adequado para extração e determinação de espécies de mercúrio através da aplicação em materiais de referência certificados de fígado de peixe (DOLT-3) e músculo de peixe (DORM-2), apresentando boas concordâncias com os valores certificados e desvio padrão relativo inferior a 9,5%. Os limites de detecção foram de 0,06 e 0,12 µg g-1 para CH3Hg+ e Hg2+, respectivamente. Além disso, foi observado um significativo efeito de matriz e, por isso, a calibração foi feita com curvas preparadas com o extrato da MSPD. O método mostrou boa concordância na comparação entre a soma da concentração das espécies e a concentração de mercúrio total determinada por espectrometria de massas com plasma indutivamente acoplado com geração de vapor frio (CVG-ICP-MS), após digestão assistida por micro-ondas (MAD) em peixes do tipo atum (Thunnus thynnus), cação anjo (Squatina squatina) e cação viola (Rhinobatos blochii.).

Characterisation and source identification of selected pollutants in house dust

House dust is a heterogeneous matrix, which contains a number of biological materials and particulate matter gathered from several sources. It is the accumulation of a number of semi-volatile and non-volatile contaminants. The contaminants are trapped and preserved. Therefore, house dust can be viewed as an archive of both the indoor and outdoor air pollution. There is evidence to show that on average, people tend to stay indoors most of the time and this increases exposure to house dust. The aims of this investigation were to: " assess the levels of Polycyclic Aromatic Hydrocarbons (PAHs), elements and pesticides in the indoor environment of the Brisbane area; " identify and characterise the possible sources of elemental constituents (inorganic elements), PAHs and pesticides by means of Positive Matrix Factorisation (PMF); and " establish the correlations between the levels of indoor air pollutants (PAHs, elements and pesticides) with the external and internal characteristics or attributes of the buildings and indoor activities by means of multivariate data analysis techniques. The dust samples were collected during the period of 2005-2007 from homes located in different suburbs of Brisbane, Ipswich and Toowoomba, in South East Queensland, Australia. A vacuum cleaner fitted with a paper bag was used as a sampler for collecting the house dust. A survey questionnaire was filled by the house residents which contained information about the indoor and outdoor characteristics of their residences. House dust samples were analysed for three different pollutants: Pesticides, Elements and PAHs. The analyses were carried-out for samples of particle size less than 250 µm. The chemical analyses for both pesticides and PAHs were performed using a Gas Chromatography Mass Spectrometry (GC-MS), while elemental analysis was carried-out by using Inductively-Coupled Plasma-Mass Spectroscopy (ICP-MS). The data was subjected to multivariate data analysis techniques such as multi-criteria decision-making procedures, Preference Ranking Organisation Method for Enrichment Evaluations (PROMETHEE), coupled with Geometrical Analysis for Interactive Aid (GAIA) in order to rank the samples and to examine data display. This study showed that compared to the results from previous works, which were carried-out in Australia and overseas, the concentrations of pollutants in house dusts in Brisbane and the surrounding areas were relatively very high. The results of this work also showed significant correlations between some of the physical parameters (types of building material, floor level, distance from industrial areas and major road, and smoking) and the concentrations of pollutants. Types of building materials and the age of houses were found to be two of the primary factors that affect the concentrations of pesticides and elements in house dust. The concentrations of these two types of pollutant appear to be higher in old houses (timber houses) than in the brick ones. In contrast, the concentrations of PAHs were noticed to be higher in brick houses than in the timber ones. Other factors such as floor level, and distance from the main street and industrial area, also affected the concentrations of pollutants in the house dust samples. To apportion the sources and to understand mechanisms of pollutants, Positive Matrix Factorisation (PMF) receptor model was applied. The results showed that there were significant correlations between the degree of concentration of contaminants in house dust and the physical characteristics of houses, such as the age and the type of the house, the distance from the main road and industrial areas, and smoking. Sources of pollutants were identified. For PAHs, the sources were cooking activities, vehicle emissions, smoking, oil fumes, natural gas combustion and traces of diesel exhaust emissions; for pesticides the sources were application of pesticides for controlling termites in buildings and fences, treating indoor furniture and in gardens for controlling pests attacking horticultural and ornamental plants; for elements the sources were soil, cooking, smoking, paints, pesticides, combustion of motor fuels, residual fuel oil, motor vehicle emissions, wearing down of brake linings and industrial activities.

Generation and characterisation of Cisplatin-resistant non-small cell lung cancer cell lines displaying a stem-like signature

Introduction: Inherent and acquired cisplatin resistance reduces the effectiveness of this agent in the management of non-small cell lung cancer (NSCLC). Understanding the molecular mechanisms underlying this process may result in the development of novel agents to enhance the sensitivity of cisplatin. Methods: An isogenic model of cisplatin resistance was generated in a panel of NSCLC cell lines (A549, SKMES-1, MOR, H460). Over a period of twelve months, cisplatin resistant (CisR) cell lines were derived from original, age-matched parent cells (PT) and subsequently characterized. Proliferation (MTT) and clonogenic survival assays (crystal violet) were carried out between PT and CisR cells. Cellular response to cisplatin-induced apoptosis and cell cycle distribution were examined by FACS analysis. A panel of cancer stem cell and pluripotent markers was examined in addition to the EMT proteins, c-Met and β-catenin. Cisplatin-DNA adduct formation, DNA damage (γH2AX) and cellular platinum uptake (ICP-MS) was also assessed. Results: Characterisation studies demonstrated a decreased proliferative capacity of lung tumour cells in response to cisplatin, increased resistance to cisplatin-induced cell death, accumulation of resistant cells in the G0/G1 phase of the cell cycle and enhanced clonogenic survival ability. Moreover, resistant cells displayed a putative stem-like signature with increased expression of CD133+/CD44+cells and increased ALDH activity relative to their corresponding parental cells. The stem cell markers, Nanog, Oct-4 and SOX-2, were significantly upregulated as were the EMT markers, c-Met and β-catenin. While resistant sublines demonstrated decreased uptake of cisplatin in response to treatment, reduced cisplatin-GpG DNA adduct formation and significantly decreased γH2AX foci were observed compared to parental cell lines. Conclusion: Our results identified cisplatin resistant subpopulations of NSCLC cells with a putative stem-like signature, providing a further understanding of the cellular events associated with the cisplatin resistance phenotype in lung cancer. © 2013 Barr et al.

Zircon chronochemistry of high heat-producing granites in Queensland and Europe

High heat-producing granites (HHPGs) are reservoir rocks for enhanced geothermal systems (EGS), yet the origins of their anomalous chemistry remain poorly understood. To gain a better understanding of the characteristic distribution of elemental depletions and enrichments (focussing on U, Th & K) within granite suites of different heritage and tectonic setting, and the processes that lead to these enrichments, we are undertaking a systematic accessory-mineral chronochemical study of two suites of S- and I-type granites in northern Queensland, as well as two archetypal HHPGs in Cornwall, England (S-type) and Soultz-sous- Forêts, France (I-type). Novel zircon LA-ICP-MS chronochemical methods will later be underpinned by a systematic petrographic, scanning electron microscope (SEM), and electron microprobe (EPMA) study of all the REE-Y-Th-U-rich accessory minerals to fully characterise how the composition, textural distributions and associations change with rock chemistry between and among the suites. Preliminary results indicate that zircons with inherited ages do not have anomalously high U (>1000 ppm) & Th (>400 ppm) values (Ahrens, 1965). Instead, enrichment in these HPE is seen in zircons dated to around the time of magmatic emplacement. These results indicate that enrichment arose primarily through fractional crystallisation of the granitic magmas. Our results support the suggestion that a source pre-enriched in the HPEs does not appear to be fundamental for the formation of all HHPGs. Instead fractional crystallisation processes, and the accessory minerals formed in magmas of differing initial compositions, are the key controls on the levels of enrichment observed (e.g. Champion & Chappell, 1992; Chappell & Hine, 2006). One implication is that the most fractionated granites may not be the most enriched in the HPEs and therefore prospective to future EGS development.

Identification and elimination of a matrix-induced systematic error in LA–ICP–MS 206Pb/238U dating of zircon

Black et al. (2004) identified a systematic difference between LA–ICP–MS and TIMS measurements of 206Pb/238U in zircons, which they correlated with the incompatible trace element content of the zircon. We show that the offset between the LA–ICP–MS and TIMS measured 206Pb/238U correlates more strongly with the total radiogenic Pb than with any incompatible trace element. This suggests that the cause of the 206Pb/238U offset is related to differences in the radiation damage (alpha dose) between the reference and unknowns. We test this hypothesis in two ways. First, we show that there is a strong correlation between the difference in the LA–ICP–MS and TIMS measured 206Pb/238U and the difference in the alpha dose received by unknown and reference zircons. The LA–ICP–MS ages for the zircons we have dated can be as much as 5.1% younger than their TIMS age to 2.1% older, depending on whether the unknown or reference received the higher alpha dose. Second, we show that by annealing both reference and unknown zircons at 850 °C for 48 h in air we can eliminate the alpha-dose-induced differences in measured 206Pb/238U. This was achieved by analyzing six reference zircons a minimum of 16 times in two round robin experiments: the first consisting of unannealed zircons and the second of annealed grains. The maximum offset between the LA–ICP–MS and TIMS measured 206Pb/238U for the unannealed zircons was 2.3%, which reduced to 0.5% for the annealed grains, as predicted by within-session precision based on counting statistics. Annealing unknown zircons and references to the same state prior to analysis holds the promise of reducing the 3% external error for the measurement of 206Pb/238U of zircon by LA–ICP–MS, indicated by Klötzli et al. (2009), to better than 1%, but more analyses of annealed zircons by other laboratories are required to evaluate the true potential of the annealing method.

Timing and source constraints on the relationship between mafic and felsic intrusions in the Emeiashan large igneous province

Several I- and A-type granite, syenite plutons and spatially associated, giant Fe–Ti–V deposit-bearing mafic ultramafic layered intrusions occur in the Pan–Xi(Panzhihua–Xichang) area within the inner zone of the Emeishan large igneous province (ELIP). These complexes are interpreted to be related to the Emeishan mantle plume. We present LA-ICP-MS and SIMS zircon U–Pb ages and Hf–Nd isotopic compositions for the gabbros, syenites and granites from these complexes. The dating shows that the age of the felsic intrusive magmatism (256.2 ± 3.0–259.8 ± 1.6 Ma) is indistinguishable from that of the mafic intrusive magmatism (255.4 ± 3.1–259.5 ± 2.7 Ma) and represents the final phase of a continuous magmatic episode that lasted no more than 10 Myr. The upper gabbros in the mafic–ultramafic intrusions are generally more isotopically enriched (lower eNd and eHf) than the middle and lower gabbros, suggesting that the upper gabbros have experienced a higher level of crustal contamination than the lower gabbros. The significantly positive eHf(t) values of the A-type granites and syenites (+4.9 to +10.8) are higher than those of the upper gabbros of the associated mafic intrusion, which shows that they cannot be derived by fractional crystallization of these bodies. They are however identical to those of the mafic enclaves (+7.0 to +11.4) and middle and lower gabbros, implying that they are cogenetic. We suggest that they were generated by fractionation of large-volume, plume-related basaltic magmas that ponded deep in the crust. The deep-seated magma chamber erupted in two stages: the first near a density minimum in the basaltic fractionation trend and the second during the final stage of fractionation when the magma was a low density Fe-poor, Si-rich felsic magma. The basaltic magmas emplaced in the shallowlevel magma chambers differentiated to form mafic–ultramafic layered intrusions accompanied by a small amount of crustal assimilation through roof melting. Evolved A-type granites (synenites and syenodiorites) were produced dominantly by crystallization in the deep crustal magma chamber. In contrast, the I-type granites have negative eNd(t) [-6.3 to -7.5] and eHf(t) [-1.3 to -6.7] values, with the Nd model ages (T Nd DM2) of 1.63-1.67 Ga and Hf model ages (T Hf DM2) of 1.56-1.58 Ga, suggesting that they were mainly derived from partial melting of Mesoproterozoic crust. In combination with previous studies, this study also shows that plume activity not only gave rise to reworking of ancient crust, but also significant growth of juvenile crust in the center of the ELIP.

Two cycles of voluminous pyroclastic volcanism and sedimentation related to episodic granite emplacement during the late Archean : Eastern Yilgarn Craton, Western Australia

The thick piles of late-Archean volcaniclastic sedimentary successions that overlie the voluminous greenstone units of the eastern Yilgarn Craton, Western Australia, record the important transition from the cessation in mafic-ultramafic volcanism to cratonisation between about 2690 and 2655 Ma. Unfortunately, an inability to clearly subdivide the superficially similar sedimentary successions and correlate them between the various geological terranes and domains of the eastern Yilgarn Craton has led to uncertainty about the timing and nature of the region's palaeogeographic and palaeotectonic evolution. Here, we present the results of some 2025 U–Pb laser-ablation-ICP-MS analyses and 323 Sensitive High-Resolution Ion Microprobe (SHRIMP) analyses of detrital zircons from 14 late-Archean felsic clastic successions of the eastern Yilgarn Craton, which have enabled correlation of clastic successions. The results of our data, together with those compiled from previous studies, show that the post-greenstone sedimentary successions include two major cycles that both commenced with voluminous pyroclastic volcanism and ended with widespread exhumation and erosion associated with granite emplacement. Cycle One commences with an influx of rapidly reworked feldspar-rich pyroclastic debris. These units, here-named the Early Black Flag Group, are dominated by a single population of detrital zircons with an average age of 2690–2680 Ma. Thick (up to 2 km) dolerite bodies, such as the Golden Mile Dolerite, intrude the upper parts of the Early Black Flag Group at about 2680 Ma. Incipient development of large granite domes during Cycle One created extensional basins predominantly near their southeastern and northwestern margins (e.g., St Ives, Wallaby, Kanowna Belle and Agnew), into which the Early Black Flag Group and overlying coarse mafic conglomerate facies of the Late Black Flag Group were deposited. The clast compositions and detrital-zircon ages of the late Black Flag Group detritus match closely the nearby and/or stratigraphically underlying successions, thus suggesting relatively local provenance. Cycle Two involved a similar progression to that observed in Cycle One, but the age and composition of the detritus were notably different. Deposition of rapidly reworked quartz-rich pyroclastic deposits dominated by a single detrital-zircon age population of 2670–2660 Ma heralded the beginning of Cycle Two. These coarse-grained quartz-rich units, are name here the Early Merougil Group. The mean ages of the detrital zircons from the Early Merougil Group match closely the age of the peak in high-Ca (quartz-rich) granite magmatism in the Yilgarn Craton and thus probably represent the surface expression of the same event. Successions of the Late Merougil Group are dominated by coarse felsic conglomerate with abundant volcanic quartz. Although the detrital zircons in these successions have a broad spread of age, the principal sub-populations have ages of about 2665 Ma and thus match closely those of the Early Merougil Group. These successions occur most commonly at the northwestern and southeastern margins of the granite batholiths and thus are interpreted to represent resedimented units dominted by the stratigraphically underlying packages of the Early Merougil Group. The Kurrawang Group is the youngest sedimentary units identified in this study and is dominated by polymictic conglomerate with clasts of banded iron formation (BIF), granite and quartzite near the base and quartz-rich sandstone units containing detrital zircons aged up to 3500 Ma near the top. These units record provenance from deeper and/or more-distal sources. We suggest here that the principal driver for the major episodes of volcanism, sedimentation and deformation associated with basin development was the progressive emplacement of large granite batholiths. This interpretation has important implication for palaeogeographic and palaeotectonic evolution of all late-Archean terranes around the world.

Low delta18O zircon grains in the Neoarchean Rum Jungle Complex, northern Australia: An indicator of emergent continental crust

The timing of widespread continental emergence is generally considered to have had a dramatic effect on the hydrological cycle, atmospheric conditions, and climate. New secondary ion mass spectrometry (SIMS) oxygen and laser-ablation–multicollector–inductively coupled plasma–mass spectrometry (LA-MC-ICP-MS) Lu-Hf isotopic results from dated zircon grains in the granitic Neoarchean Rum Jungle Complex provide a minimum time constraint on the emergence of continental crust above sea level for the North Australian craton. A 2535 ± 7 Ma monzogranite is characterized by magmatic zircon with slightly elevated δ18O (6.0‰–7.5‰ relative to Vienna standard mean ocean water [VSMOW]), consistent with some contribution to the magma from reworked supracrustal material. A supracrustal contribution to magma genesis is supported by the presence of metasedimentary rock enclaves, a large population of inherited zircon grains, and subchondritic zircon Hf (εHf = −6.6 to −4.1). A separate, distinct crustal source to the same magma is indicated by inherited zircon grains that are dominated by low δ18O values (2.5‰–4.8‰, n = 9 of 15) across a range of ages (3536–2598 Ma; εHf = −18.2 to +0.4). The low δ18O grains may be the product of one of two processes: (1) grain-scale diffusion of oxygen in zircon by exchange with a low δ18O magma or (2) several episodes of magmatic reworking of a Mesoarchean or older low δ18O source. Both scenarios require shallow crustal magmatism in emergent crust, to allow interaction with rocks altered by hydrothermal meteoric water in order to generate the low δ18O zircon. In the first scenario, assimilation of these altered rocks during Neoarchean magmatism generated low δ18O magma with which residual detrital zircons were able to exchange oxygen, while preserving their U-Pb systematics. In the second scenario, wholesale melting of the altered rocks occurred in several distinct events through the Mesoarchean, generating low δ18O magma from which zircon crystallized. Ultimately, in either scenario, the low δ18O zircons were entrained as inherited grains in a Neoarchean granite. The data suggest operation of a modern hydrological cycle by the Neoarchean and add to evidence for the increased emergence of continents by this time

Evolution of a ~2.7 Ga large igneous province: A volcanological, geochemical and geochronological study of the Agnew Greenstone Belt, and new regional correlations for the Kalgoorlie Terrane (Yilgarn Craton, Western Australia)

The thick package of ~2.7 Ga mafic and ultramafic lavas and intrusions preserved among the Neoarchean of the Kalgoorlie Terrene in Western Australia provides valuable insight into geological processes controlling the most prodigious episode of growth and preservation of juvenile continental crust in Earth’s history. Limited exposure of these rocks results in uncertainty about their age, physical and chemical characteristics, and stratigraphic relationships. This in turn prevents confident correlation of regional occurrences of mafic and ultramafic successions (both intrusive and extrusive) and hinders the interpretation of tectonic setting and magmatic evolution. A recent stratigraphic drilling program of the Neoarchean stratigraphy of the Agnew Greenstone Belt in Western Australia has provided continuous exposures through a c. 7 km thick sequence of mafic and ultramafic units. In this study, we present a volcanological, lithogeochemical and chronological study of the Agnew Greenstone Belt, and provide the first pre-2690 Ma regional correlation across the Kalgoorlie Terrane. The Agnew Greenstone Belt records ~30 m.y. of episodic ultramafic-mafic magmatism that includes two cycles, each defined by a komatiite that is overlain by units that become more evolved and contaminated with time. The sequence is divided into nine conformable packages, each consisting of stacked subaqueous lava flows and comagmatic intrusions, as well as two sills without associated extrusions. Lavas, with the exception of intercalations between two units, form a layer-cake stratigraphy and were likely erupted from a system of fissures tapping the same magma source. The komatiites are not contaminated by continental crust ([La/Sm]PM ~0.7) and are of the Al-undepleted Munro-type. Crustal contamination is evident in many units (Songvang Basalt, Never Can Tell Basalt, Redeemer Basalt, and Turrett Dolerite), as judged by [La/Sm]>1, negative Nb and Ti anomalies, and geochemical mixing trends towards felsic contaminants. Crystal fractionation was also significant, with early olivine and chromite (Mg#>65) followed by plagioclase and clinopyroxene removal (Mg<65), and in the most evolved case, titanomagnetite accumulation. Three new TIMS dates on granophyric zones of mafic sills and one ICP-MS date from an interflow felsic tuff are presented and used for regional stratigraphic correlation. Cycle I magmatism began at ~2720 Ma and ended ~2705 Ma, whereas cycle II began ~2705 Ma and ended at 2690.7±1.2 Ma. Regional correlations indicate the western Kalgoorlie Terrane consists of a remarkably similar stratigraphy that can be recognised at Agnew, Ora Banda and Coolgardie, whereas the eastern part of the terrane (e.g., Kambalda Domain) does not include cycle I, but correlates well with cycle II. This research supports an autochthonous model of greenstone formation, in which one large igneous province, represented by two complete cycles, is constructed on sialic crust. New stratigraphic correlations for the Kalgoorlie Terrane indicate that many units can be traced over distances >100 km, which has implications for exploration targeting for stratigraphically hosted ultramafic Ni and VMS deposits.

Determination of refractive and volatile elements in sediment using laser ablation inductively coupled plasma mass spectrometry

Wet-milling protocol was employed to produce pressed powder tablets with excellent cohesion and homogeneity suitable for laser ablation (LA) analysis of volatile and refractive elements in sediment. The influence of sample preparation on analytical performance was also investigated, including sample homogeneity, accuracy and limit of detection. Milling in volatile solvent for 40 min ensured sample is well mixed and could reasonably recover both volatile (Hg) and refractive (Zr) elements. With the exception of Cr (−52%) and Nb (+26%) major, minor and trace elements in STSD-1 and MESS-3 could be analysed within ±20% of the certified values. Comparison of the method with total digestion method using HF was tested by analysing 10 different sediment samples. The laser method recovers significantly higher amounts of analytes such as Ag, Cd, Sn and Sn than the total digestion method making it a more robust method for elements across the periodic table. LA-ICP-MS also eliminates the interferences from chemical reagents as well as the health and safety risks associated with digestion processes. Therefore, it can be considered as an enhanced method for the analysis of heterogeneous matrices such as river sediments.

SU-8-Based Microchips for Capillary Electrophoresis and Electrospray Ionization Mass Spectrometry

Miniaturization of analytical instrumentation is attracting growing interest in response to the explosive demand for rapid, yet sensitive analytical methods and low-cost, highly automated instruments for pharmaceutical and bioanalyses and environmental monitoring. Microfabrication technology in particular, has enabled fabrication of low-cost microdevices with a high degree of integrated functions, such as sample preparation, chemical reaction, separation, and detection, on a single microchip. These miniaturized total chemical analysis systems (microTAS or lab-on-a-chip) can also be arrayed for parallel analyses in order to accelerate the sample throughput. Other motivations include reduced sample consumption and waste production as well as increased speed of analysis. One of the most promising hyphenated techniques in analytical chemistry is the combination of a microfluidic separation chip and mass spectrometer (MS). In this work, the emerging polymer microfabrication techniques, ultraviolet lithography in particular, were exploited to develop a capillary electrophoresis (CE) separation chip which incorporates a monolithically integrated electrospray ionization (ESI) emitter for efficient coupling with MS. An epoxy photoresist SU-8 was adopted as structural material and characterized with respect to its physicochemical properties relevant to chip-based CE and ESI/MS, namely surface charge, surface interactions, heat transfer, and solvent compatibility. As a result, SU-8 was found to be a favorable material to substitute for the more commonly used glass and silicon in microfluidic applications. In addition, an infrared (IR) thermography was introduced as direct, non-intrusive method to examine the heat transfer and thermal gradients during microchip-CE. The IR data was validated through numerical modeling. The analytical performance of SU-8-based microchips was established for qualitative and quantitative CE-ESI/MS analysis of small drug compounds, peptides, and proteins. The CE separation efficiency was found to be similar to that of commercial glass microchips and conventional CE systems. Typical analysis times were only 30-90 s per sample indicating feasibility for high-throughput analysis. Moreover, a mass detection limit at the low-attomole level, as low as 10E+5 molecules, was achieved utilizing MS detection. The SU-8 microchips developed in this work could also be mass produced at low cost and with nearly identical performance from chip to chip. Until this work, the attempts to combine CE separation with ESI in a chip-based system, amenable to batch fabrication and capable of high, reproducible analytical performance, have not been successful. Thus, the CE-ESI chip developed in this work is a substantial step toward lab-on-a-chip technology.

Role of spectator ions in influencing the properties of dopant-free ZnO nanocrystals

Towards fundamental studies and potential applications, achieving precise control over the generation of defects in pure ZnO nanocrystals has been always intriguing. Herein, we explored the rote of spectator ions (Co2+ and Ni2+) in influencing the functional properties of ZnO nanocrystals. The crystalline quality, phase purity, and composition of as-prepared samples were thoroughly established by powder X-ray diffraction, electron microscopy (TEM and STEM), and by Raman and X-ray photoelectron spectroscopies (XPS). Despite the presence of Co2+ and Ni2+ ions in the reaction mixture, STEM-energy dispersive spectroscopy (EDS), XPS analysis, and inductively-coupled plasma mass spectrometry (ICP-MS) revealed that the ZnO nanocrystals formed are dopant-free. Even so, their luminescence and magnetic properties were substantially different from those of pure ZnO nanocrystals synthesized using a similar methodology. We attribute the origin of these properties to the defects associated with ZnO nanocrystals generated under different but optimized conditions.

Photoactivated cytotoxicity of ferrocenyl-terpyridine oxovanadium(IV) complexes of curcuminoids

Oxovanadium(IV) complexes, viz. VO(Fc-tpy)(Curc)](ClO4) (1), VO(Fc-tpy)(bDHC)](ClO4) (2), VO(Fc-tpy)(bDMC)](ClO4) (3) and VO(Ph-tpy)(Curc)](ClO4) (4), of 4'-ferrocenyl-2,2':6',2 `'-terpyridine (Fc-tpy) and 4'-phenyl-2,2':6',2 `'-terpyridine (Ph-tpy) and monoanionic curcumin (Curc), bis-dehydroxycurcmin (bDHC) and bis-demethoxycurcumin (bDMC) were prepared, characterized and their photo-induced DNA cleavage activity and photocytotoxicity in visible light studied. The ferrocenyl complexes 1-3 showed an intense metal-to-ligand charge transfer band near 585 nm in DMF and displayed Fc(+)/Fc and V(IV)/V(III) redox couples near 0.65 V and -1.05 V vs. SCE in DMF-0.1 M TBAP. The complexes as avid binders to calf thymus DNA showed significant photocleavage of plasmid DNA in red light of 647 nm forming (OH)-O-center dot radicals. The complexes showed photocytotoxicity in HeLa and Hep G2 cancer cells in visible light of 400-700 nm with low dark toxicity. ICP-MS and fluorescence microscopic studies exhibited significant cellular uptake of the complexes within 4 h of treatment with complexes. The treatment with complex 1 resulted in the formation of reactive oxygen species inside the HeLa cells which was evidenced from the DCFDA assay. (C) 2014 Elsevier Masson SAS. All rights reserved.