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.

In search of a hidden long-term isolated sub-chondritic 142Nd/144Nd reservoir in the deep mantle : implications for the Nd isotope systematics of the Earth

Here we search for evidence of the existence of a sub-chondritic 142Nd/144Nd reservoir that balances the Nd isotope chemistry of the Earth relative to chondrites. If present, it may reside in the source region of deeply sourced mantle plume material. We suggest that lavas from Hawai’i with coupled elevations in 186Os/188Os and 187Os/188Os, from Iceland that represent mixing of upper mantle and lower mantle components, and from Gough with sub-chondritic 143Nd/144Nd and high 207Pb/206Pb, are favorable samples that could reflect mantle sources that have interacted with an Early-Enriched Reservoir (EER) with sub-chondritic 142Nd/144Nd. High-precision Nd isotope analyses of basalts from Hawai’i, Iceland and Gough demonstrate no discernable 142Nd/144Nd deviation from terrestrial standards. These data are consistent with previous high-precision Nd isotope analysis of recent mantle-derived samples and demonstrate that no mantle-derived material to date provides evidence for the existence of an EER in the mantle. We then evaluate mass balance in the Earth with respect to both 142Nd/144Nd and 143Nd/144Nd. The Nd isotope systematics of EERs are modeled for different sizes and timing of formation relative to ε143Nd estimates of the reservoirs in the μ142Nd = 0 Earth, where μ142Nd is ((measured 142Nd/144Nd/terrestrial standard 142Nd/144Nd)−1 * 10−6) and the μ142Nd = 0 Earth is the proportion of the silicate Earth with 142Nd/144Nd indistinguishable from the terrestrial standard. The models indicate that it is not possible to balance the Earth with respect to both 142Nd/144Nd and 143Nd/144Nd unless the μ142Nd = 0 Earth has a ε143Nd within error of the present-day Depleted Mid-ocean ridge basalt Mantle source (DMM). The 4567 Myr age 142Nd–143Nd isochron for the Earth intersects μ142Nd = 0 at ε143Nd of +8 ± 2 providing a minimum ε143Nd for the μ142Nd = 0 Earth. The high ε143Nd of the μ142Nd = 0 Earth is confirmed by the Nd isotope systematics of Archean mantle-derived rocks that consistently have positive ε143Nd. If the EER formed early after solar system formation (0–70 Ma) continental crust and DMM can be complementary reservoirs with respect to Nd isotopes, with no requirement for significant additional reservoirs. If the EER formed after 70 Ma then the μ142Nd = 0 Earth must have a bulk ε143Nd more radiogenic than DMM and additional high ε143Nd material is required to balance the Nd isotope systematics of the Earth.

Caracterização ambiental da bacia hidrogáfica do Rio São Domingos a partir da análise geoquímica e isotópica Pb/Pb

A bacia hidrográfica do rio São Domingos constitui uma das sub-bacias do rio Muriaé pertencente ao sistema Paraíba do Sul e, tem seus limites coincidentes com os limites do município de São José de Ubá, sendo este o segundo maior produtor de tomate do estado do Rio de Janeiro, com sua principal fonte econômica baseada na agropecuária. Este tipo de atividade resulta em utilização de produtos químicos nas lavouras e juntamente a ocupação inadequada resulta em modificação das paisagens e da mata nativa, resultando em diversos tipos de impactos no ambiente. Neste estudo foram abordados os impactos relacionados a concentração de metais e sua proveniência através das assinaturas isotópicas Pb/Pb, utilizando para tal o procedimento analítico de lixiviação dos sedimentos de corrente e abertura total de rochas para a obtenção de razões isotópicas e concentrações de metais por ICP-MS. Os resultados mostraram que as contribuições nos sedimentos de corrente se dão a partir de cinco fontes compreendidos no intervalo de assinatura isotópica 206Pb/207Pb 1,1229 e 1,1949, representadas em intervalos bem definidos. Por correlação com as respectivas concentrações se observa que, preferencialmente, existe maior influência das rochas do embasamento, seguido de atividade antrópicas como a urbanização e disposição de lixo doméstico. As maiores concentrações estão associadas ao cobre, chumbo, estrôncio, níquel e zinco. Contudo todas as concentrações de metais obtidas se encontram abaixo da legislação vigente. Desta forma a contaminação antrópica é limitada a regiões de maior densidade populacional e as influências naturais predominam na área da bacia.

Estudos de metais pesados e isótopos de Pb nos sedimentos da Baía de Sepetiba baseados em geoquímica e na distribuição pelas possíveis áreas fontes

A Baia de Sepetiba é uma laguna costeira separada do oceano por uma ilha barreira. Localiza-se a 60 km da cidade do Rio de Janeiro, em uma importante região geoeconômica do Brasil. O objetivo deste trabalho foi avaliar a distribuição espacial da contaminação dos metais Cu, Pb, V, Cr, Cd, Co, Ni e Zn nos sedimentos da Baia. O mapa das concentrações elaborado pelo método de lixiviação permitiu caracterizar anomalias ao entorno da foz do Rio Guandu, na área da Coroa Grande, do Porto de Itaguaí, da Ilha do Martins, e anomalias ao longo de faixa com direção NW-SE. Os resultados das concentrações totais indicam contaminação por Zn, Cd, próximo a Ilha da Madeira com Pb e Cr associados e Cu e Zn na Restinga de Marambaia, com Ni, Pb e Cr associados. Os resultados dos isótopos de Pb para as razões de 206Pb/207Pb entre 1,23 e 1,27 representam os resíduos industriais e ocorrem em duas áreas: na parte leste da Restinga e entre as Ilhas de Jaguanum e Itacuruçá. A leste/sudeste destas ilhas foi reportada uma razão ainda mais alta (1.30), ainda não identificável na literatura. As correntes marinhas desempenham a redistribuição dos sedimentos e metais associados na Baia, com transporte de oeste para leste da pluma sedimentar descarregada pelos rios. Os principais causadores da poluição da Baia de Sepetiba são uma pilha de rejeito de Zn abandonada, resíduos industriais e domésticos não tratados de forma eficaz, poluentes atmosféricos de siderúrgicas e veículos, e por ventura resíduos de atividades navais e militares.

Traçadores isotópicos (Pb) e concentrações de metais em sedimentos superficiais: ferramentas na caracterização da poluição no setor oeste da baía de Sepetiba-RJ (SE do Brasil)

Este estudo teve como objetivo principal utilizar os teores de elementos-traço e análise isotópica de Pb (204Pb,206Pb,207Pb,208Pb) como ferramentas na caracterização da poluição da Baía de Sepetiba-RJ. As coletas de sedimento superficiais de fundo foram realizadas em três campanhas, em novembro de 2010, no setor oeste da Baía de Sepetiba RJ. A malha amostral é composta por 66 amostras (BSEP 001 a BSEP 066) coletadas com busca-fundo Van Veen. O pré-processamento das amostras ocorreu no Laboratório Geológico de Preparação de Amostras do Departamento de Geologia da Universidade do Estado do Rio de Janeiro. A digestão parcial das amostras de sedimento (< 0.072 mm) para obtenção do teor parcial dos elementos-traço (Ag, As, Cd, Co, Cr, Cu, Li, Mn, Ni, Pb, Sr, U, Zn) e de isótopo de Pb (lixiviação) foi executada no Laboratório de Geoquímica Analítica do Instituto de Geociências da UNICAMP e a leitura foi executada através do ICP-MS. Já as análises das concentrações totais dos elementos-traço (inclusive, Hg) e de isótopos de Pb (dissolução total) foram realizadas no laboratório ACTLABS (Ontário-Canadá) através do ICP Varian Vista. As leituras isotópicas foram feitas somente nas amostras que apresentaram concentrações parciais de Pb, acima de 0,5 g/g, totalizando 21 estações. Pôde-se constatar a existência de um enriquecimento de elementos-traço no setor oeste da Baía de Sepetiba. As médias dos teores totais de Ag (0,4 g/g), Cd (0,76 g/g), Cu (62,59 g/g), Li (43,29 g/g), Ni (16,65 g/g), Pb (20,08 g/g), Sr (389,64 g/g) e Zn (184,82 g/g) excederam os limites recomendados ou valores naturais. Isto pode ser reflexo da influência antrópica na região, principalmente relacionada à atividade de dragagem e à permanência dos resíduos de minério da desativada companhia de minério Ingá, na Ilha da Madeira. Os mapas de distribuição da concentração dos metais-traço destacaram a presença de vários sítios de deposição ao longo do setor oeste da baía de Sepetiba, com destaque para a região entre a porção centro oeste da Ilha de Itacuruça e o continente; Saco da Marambaia e Ponta da Pombeba; e porção oeste da Ponta da Marambaia. As razões isotópicas 206Pb/207Pb da área estudada variaram entre 1,163 a 1,259 para dissolução total e 1,1749-1,1877 para técnica de lixiviação, valores considerados como assinaturas de sedimentos pós-industriais ou comparados à assinatura de gasolina. Ainda sobre a técnica de lixiviação, destaca-se que os sedimentos superficiais do setor oeste (206Pb/207Pb: 1,1789) da baía de Sepetiba apresentaram uma assinatura uniforme e menos radiogênica do que setor leste (206Pb/207Pb: 1,2373 e 1,2110) desta baía. Através da assinatura isotópica de Pb encontrada nesta região é possível destacar a pouca contribuição das águas oceânicas para esse sistema, entretanto, a circulação interna intensa das águas da baía permite a homogeneização destas. O emprego destes tipos de ferramentas no monitoramento ambiental da área mostrou-se bastante eficiente, sendo importante a continuidade desta abordagem de pesquisa a fim de auxiliar na implementação de um plano de manejo local.

Estudo isotópico e geoquímico dos sedimentos costeiros da Costa Verde do Estado do Rio de Janeiro para identificação de atividades antrópicas

A Costa Verde se localiza no estado do Rio Janeiro, onde também está localizada a Ilha Grande, importante polo turístico do estado. É composta pelas baías Sepetiba e Ilha Grande, que podem ser compartimentadas em diversas enseadas. As principais enseadas são Sepetiba, Marambaia, Mangaratiba, Angra dos Reis, Ribeira, Frade e Paraty. O presente estudo foi realizado nas enseadas de Mangaratiba, Angra dos Reis e Ribeira e foram compilados dados de Sepetiba e Marambaia estudado por outros autores. O objetivo do estudo destas enseadas foi identificar os metais e suas fontes e os mecanismos que os controlam, além de propor novos parâmetros de concentração de metais que indiquem processos de contaminação. O método utilizado foi a coleta de sedimento de fundo através da utilização de Van Veen e analisados por digestão total em espectrômetro de massa da qual se obteve a concentração dos elementos Ca, Cd, Co, Cr, Cu, K, Pb, Na, Ni, Sr, S, U, V e Zn, além das razões isotópicas de chumbo, com prioridade da razão 206Pb/207Pb. Foram obtidos resultados que indicam que a enseada de Mangaratiba apresenta as maiores concentrações de metais e com predominante contribuição antrópica cujas fontes são, os empreendimentos localizados na costa dessa enseada, incluindo o TEBIG. A enseada de Angra dos Reis também apresenta concentrações elevadas de metais, provenientes de efluentes domésticos, rejeito industrial ao qual se inclui o estaleiro Verolme e com forte controle do embasamento da enseada. A enseada da Ribeira tem seus metais fornecidos pelo porto de Bracuhy e uma fonte desconhecida que são controlados, em parte, pelos efluentes da CNAAA. Em relação a interação entre as cinco enseadas existe mútua troca de metais controlados pela dinâmica da Costa e acentuada pelo Canal de Ilha Grande (que liga as duas baias), onde a dispersão dos metais também é controlada por temperatura, fração sedimentar, profundidade e salinidade. Os principais metais relacionados às fontes antrópicas na Costa Verde são Co, Cr, Cu, Mn, Ni, Pb e Zn. As concentrações hoje apresentadas na resolução CONAMA não atendem a realidade da Costa Sul brasileira, sendo então propostos novos parâmetros de controle, menos permissivo

中子核和铅区核的结构研究

我们首先用Woods-Saxon势对一些丰中子核进行了系统的计算．计算表明在Woods-Saxon势中考虑一个对称能项，Woods-Saxon势就能够很好的描述丰中子核的密度分布，单粒子能级结构和中子质子的均方根半径．用Woods Saxon势的计算结果表明中子皮是丰中子远离β稳定线核的普遍现象。2S1/2轨道与1d 5/2轨道的交又和2s1d壳与1p壳的壳崩渍是中子晕形成的重要原因，也是中子晕与中子皮的一个重要区别．壳模型的计算能够很好的再现9《A《14和3《Z《5丰中子核的许多性质，这表明了，改进壳模型的有效相互作用，壳模型可能能够描述远离核的性质． 我们208Ti一类核和206Pb的一些性质进行了系统的壳模型计算．计算结果表明，K-H和SDI等有效相互作用对描述208Ti一类核和206Pb的高激发态仍然是有效的，计算结果也表明，如果208Hg可供利用的β衰变能比206Hg小，则可以预计208Hg的半寿命比206Hg要长.计算还证实了在反应209Bi（ρ，a )206Pb中激发的206Pb激发态结构，与205Tl低激发态结构相似，即这些态可以用h9/2轨道上的一个质子与205T1的低激发态的弱耦合来描述，此即所谓的对应的相似多重态的概念． 最后，我们对11Li等中子晕核的束缚机制提出了一种新的关联机制和讨论了用壳模型描述集体运动的方法．

西天山造山带古生代构造演化与地壳增生—来自花岗岩和蛇绿岩的证据

The Central Asian Orogen Belt (CAOB), which is different from the subductional orogen and the collisional orogen, is known as the most important site of crustal growth in the Phanerozoic, and it has been a ‘hot spot’ for studying the orogenic belts. The Chinese West Tianshan Orogen is occupying the west-southern part of the CAOB and is of great importances to understand the orogenic processes and the continental growth in the Central Asia. The West Tianshan Orogen had undergone complex tectonic evolutional processes in Paleozoic times and large volumes granitic rocks have recorded important information about these processes. Litter is known about Phanerozoic continental growth in the Western Tianshan area so far, compared with the other areas of the CAOB, such as eastern Junggar, western Junggar, Altai and Alakol. The aim of this dissertation is to set up the chronology frame of granitoids in western Tianshan, provide new evidence for the tectonic evolution and discuss the Paleozoic continental growth in this area, on the basis of the studies on the isotopic chronology, major element, trace element and Nd-Sr isotopic geochemistry of granitoids and the isotopic chronology and geochemistry of the ophiolites in this area, especially the Kule Lake ophiolites. 25 precise SHRIMP U-Pb zircon and LA-ICPMS U-Pb zircon ages have been obtained in this dissertation. The granitic rocks in western Tianshan had been formed during two periods: the granitic gneiss with an age of 896Ma, possibly representing the forming age of the Precambrian basement; the granitic rocks with ages varying from 479Ma to 247Ma, recording the Paleozoic orogenic process of western Tianshan. The granitoids in western Tianshan are composed of intermediate-basic rocks, intermediate rocks, intermediate-acid rocks and acid rocks, mainly intermediate-acid rocks and acid rocks. They are mostly granite, granodiorite, quartz syenite and monzodiorite. Different types of granitic rocks are exposed in different tectonic units. The granitoids on the northern margin of the Yili Plate mainly formed in late Paleozoic (413Ma ~ 281Ma), those with ages varying from 413Ma to 297Ma show continental arc affinities and the magnesian calc-alkalic metaluminous diorite of 281Ma display the geochemical characteristics similar to those of granites formed during the post-orogenic period. The granitiods on the southern margin of the Yili Plate include the adakite diorite of 470Ma which was formd by partial melting of thickened lower crust, the post-collisional alkali-feldspar granite of 430Ma, the volcanic arc granite of 348Ma and the Triassic post-collisional granite. The granitoids in the Central Tianshan Plate formed in 479Ma ~ 247Ma, mainly in 433Ma ~ 321Ma. The granitic rocks with ages of 479Ma ~ 321Ma are magnesian calc-alkalic to alkalic rocks with continental arc affinities. A few post-collisional granitoids of 276Ma ~ 247Ma may have inherited the geochemical characteristics of pre-existing arc magma. The granitic rocks in Southern Tianshan (northern margin of the Tarim plate) formed two stages, 420Ma ~ 411Ma and ca. 285Ma. The magnesian calcic to alkalic granites of 420Ma ~ 411Ma may formed during the extension process of the continental margin. The granite of 285Ma includes mostly ferroan calc-alkalic to alkali-calcic rocks with high SiO2 and high alkaline contents, and obviously negative anomaly of Eu, Ba, Sr, P, Ti, similar to the geochemical characteristics of the A-type granite which is formed during post-collisional extension. The Kule Lake ophiolite in southern Tianshan shows the affinity of N-MORB. A SHRIMP zircon U-Pb age of 425±8Ma has obtained for gabbros. Some zircons have given another group of 206Pb/238U age 918Ma, which may indicate the information of the pre-exist old basement rock. The small oceanic basin represented by Kule Lake ophiolite probably developed on the split northern margin of Tarim block. A model for Paleozoic tectonic evolution of the West Tianshan Orogen has been proposed here on the basis of the new results obtained in this dissertation and the previous published data. In Early Cambrian, the Terskey Ocean occurred along the North Nalati fault (NNF), and it separated the Yili plate from the Central Tianshan plate which was probably connected with the Tarim plate. The Terskey Ocean probably subducted towards south under the Central Tianshan plate and towards north under the Yili plate simultaneously. In the early stage of Late Ordovician, the Terskey Ocean had been closed, and the Yili and Central Tianshan plates collided. Meanwhile, extension happened within the joint Central Tianshan and Tarim plates gradually and the Paleo-South Tianshan Ocean had been formed. In Early Silurian, the Paleo-South Tianshan Ocean began to subduct beneath the composite Yili-Central Tianshan plate, which was intruded by volcanic arc granitoids. In Middle Silurian, the Paleo-South Tianshan Ocean, which had reached a certain width, was subducting strongly. And this subduction may have produced voluminous granitoids in the Central Tianshan plate. In the latest stage of Carboniferous, the Paleo-South Tianshan ocean closed, and the Yili-Central Tianshan plate and Tarim plate collided. In Late Cambrian, Paleo-Junggar Ocean occurred to north of the Yili plate; and started to subduct towards south under the Yili plate in Ordovician. This subduction may have produced a magma arc on the northern margin of the Yili plate. In Late Carboniferous, the Paleo-Junggar Ocean had been closed. The Yili-Central and Junggar plates amalgamated together. The West Tianhan Orogen may undergo a post-collisional collapse since Permian. And the magmatic activities may continue to early Triassic. The initial 87Sr/86Sr ration of the granitic rocks in the western Tianshan Mountains varies from 0.703226 to 0.716343, and Nd（t）from -6.50 to 2.03. The characteristics of Sr-Nd isotope indicate that the source of granitic material is not a sole source, which may be produced by mantle-crust magma mixing. In Paleozoic time, lateral growth of the continental crust along active continental margins was dominant, whereas the vertical growth of continental crust resulted from post- collisional mantle derived magmas was not obvious.

东准噶尔和尔赛斑岩铜矿特征及其形成的构造背景

Hersai porphyry copper deposit(PCD) of eastern junggar, newly discovered copper deposit, is located at the eastern segment of the Xiemisitai-Kulankazigan-Zhifang-Qiongheba Paleozoic island arc, Eastern Junggar. The Hersai PCD is developed in a intrusive complex, characterized by intensive and multiform hydrothermal alteration, including potassic alteration, silification, chloritization，sericitization，kaolinitization and carbonatization. Granodiorite, grandiorite porphyry, granite and concealed explosion breccia are hosts of the ore bodies containing veinlet and disseminated ore. Ore-bearing granite (ZK107-1-9), granodiorite (ZK107-1-9) and Ore-barren granodiorite (HES2-1) are selected to date zircon U-Pb age by SHRIMP method, and have an age of 429.4±6.4Ma ,413.0±3.4Ma and 411.1±4.8Ma, respectively, showing that they were emplaced from Late Silurian to Early Devonian. In addition, sample ZK107-1-9 has some hydrothermal zircons with a weighted mean 206Pb/238U age of 404.9±3.7Ma which is interpreted to be related to the granodiorite porphyry. Re-Os dating of five molybdenite samples yielded a weighted average model age of 408.0±2.9Ma, indicating the metallogenic epoch of the Hersai PCD. The ore-forming age is close to the petrogenic time of garnodiorite (411-413Ma), this suggests the ore-forming porphyry is most possiblely granodiorite porphyry. Systematic major - trace elements and Rb-Sr-Sm-Nd-Pb-Hf isotopic characteristics were studied. Analysis results show that these intrusives have some interesting and special characteristics, as following:1) containing both calc-alkaline rocks and high potassium calc-alkaline rocks ; 2) have some characteristics of adakite, but not totally, such as much lower La/Yb ratios and no Eu anomaly or just faint Eu anomaly; 3) have an initial 87Sr/86Sr ratios(0.703852-0.704565) similar to that of BSE, positive εNd(t) values between 6.1 and 7.4, the initial 206Pb/204Pb values (17.576-17.912), 207Pb/204Pb values (15.400-15.453) , 208Pb/204Pb values (37.252-37.466) , and high εHf(t) values (10.2-15.4) close to the value of depleted mantle. These geochemical features suggest that these igneous rocks in the Hersai area not only have some characteristics of island arc, but also some characteristics that only appear in the continental margin arc. It is suggested that Hersai PCD is formed in the subduction setting by the partial melting of young crust. These works and advancements mentioned in the paper are helpful to understand the deposit geology, geochemistry and metallogenesis of Hersai PCD. It is also significant to understand mineralization and tectonic setting in the Qiongheba area.

湘西地区上震旦统上部－下寒武统底部黑色岩系沉积学及地球化学

Widespread black chert-shales occur in the Ediacaran-Cambrian(E-C) boundary successions along the flank of Yangtze Platform, South China, remarkable changes in sedimentology, geochemistry and biology were recorded. Although extensive studies were carried out upon this boundary succession, the origin of black chert-shales still remain controversial. This paper focuses on the E-C black chert-shales in western Hunan, South China, upon which detailed depositional and geochemical changes are documented, accordingly a depositional model for black chert-shales is proposed. Stratigraphic anatomy across the depositional strike demonstrates that the shallow-water Dengying dolostone along the platform margin sharply pass basinward into the Liuchapo chert successions, which indicate syndepositional extensional faulting at depth could have occurred along the platform margin. The deep-water Niutitang phosphorite-rich black shales are either underlain by the Dengying dolostones on the platform margin toward platform interior or directly by the Liuchaopo chert successions farther basinwards. By detailed investigation, silica chimneys are firsly identified approximately in the chert along platform margin; two types of silica chimneys, including mounded and splayed/funnelized chert(generally brecciated) bodies are further sorted out. The mounded chert are exitbited by domed or hummocky surfaces on the top and irregular spongy to digitiform internal fabrics; within the silica mounds, abundant original vesicles/voids and/or channels were mostly plugged by initial chalcedony, quartze crystals with minor dolomite and bladed barite crystals. Splayed/funnelized brecciated chert “intrusion” cross-cut the uppermost dolostones capping to the horizon underneath, and are directly overlain by the Niutitang phosphorite-rich black shales. Their similarities to the silica chimneys reported from the oceanic spreading centres suggest a similar origin responsible for these unique silica bodies which is also supported by the microthermonmetric data and element geochemistry. High P, Ba, Fe contents and positive correlation between Fe and TOC concentrations in the Niutitang black shales indicate a high palaeo-productivity in the Early Cambrian ocean. The low Th/U and the high V/Cr, V/Sc, V/(V+Ni) ratios in the black shales suggest an anoxic water condition during this interval. Furthermore, Positive Eu anomalies and high Ba contents in the sediments also imply a hydrothermal influence on the formation of Niutitang black shales. To better constrain the placement of deep-water successions straddling the E-C boundary and the timing of hydrothermal silica chimneys, sensitive high-resoluton ion microprobe(SHRIMP) U-Pb dating of zircon grains from tuffs within the chert succession of Liuchapo Formation at Ganziping was conducted and yields a weighted-mean 206Pb/238Pb age at 536.6±5.5Ma, younger than E-C boundary age(542.0±0.3Ma). This age combined with carbon isotopic data is then proposed to correspond to the U-Pb age of zircons(538.2±1.5Ma) from the Zhongyicun member of Meishucun Formation at Meishucun in eastern Yunna, thus, the E-C boundary in Gazngziping was placed between the Dengying formations and Liuchapo formatioms. therefore, the silica chimneys took place at the beginning of the Cambrian period. The temporal coincidence of silica chimneys and negative excursions of δ13C and δ34Spy pairs suggest hydrothermal activities were likely responsible for the isotopic changes. Under such a circumstance, vast amounts of greenhouse gases(CO2, CH4, H2S), with highly 13C-depleted carbon and 34S-depleted sulfur would be released into the ocean and atmosphere. A positive shift in δ34Scas and Δ34S values from the late Ediacaran to the Early Cambrian could be a reflection of enhanced bacterial sulfate reduction(BSR), strengthened by the intensified oceanic anoxia stimulated by hydrothermal activities. Based on the analyses of sedimentology and geochemistry, a model- “oceanic anoxia induced by hydrothermal–volcanic activies” was proposed to responsible for the formation of black chert-shales during this E-C transition. Under this case, hydrothermal-volcanic activies could release large large amount of greenhouse into atmosphere and metal micronutrients into the ocean, which may lead to global warming, stratified ocean, thereby a high palaeoproductivity; on the other hand, the massive releasing of reduced hydrothermal fluids with abundant H2S, could have in turn enhanced the ocean anoxia. All of these were favourable the for preservation of organic matter, and subsequent extensive deposition of black silica-shales.

山东西部中生代碳酸岩和火山岩的地球化学特征及其成因研究

On account of some very peculiar features, such as extremely high Sr and Nd contents which can buffer their primary isotopic signatures against crustal contamination, deep-seated origin within mantle, and quick ascent in lithosphere, carbonatites are very suitable for deciphering the nature of sub-continental lithospheric mantle(SCLM) and receiving widespread attentions all around the world. The Mesozoic carbonatites located in western Shandong was comprehensively investigated in this dissertation. The extremely high REE concentrations, similar spider diagrams to most other carbonatites around the world and high Sr. low Mn contents of apatite from carbonatites confirm their igneous origin. The K depletion of carbonatites from this studies reflect the co-existing of carbonatite melts with pargasite+phlogopite lherzolite rather than phlogopite lherzolite. Geological characteristics and their occumng without associated silicate rocks argue against their origin of fractionation of or liquid immisibility with carbonated silicate melts. In contrast to the low S7Sr/86Sr and high l43Nd/l44Nd of other carbonatites in the world, carbonatites of this studies show EMU features with high S7Sr/86Sr and low l4jNd/144Nd ratios, which imply that this enriched nature was formed through metasomatism of enriched mantle preexisted beneath the Sino-korean craton by partial melts of subducted middle-lower crust of Yangtze craton. In addition to carbonatites, the coeval Mesozoic volcanic rocks from western Shandong were also studied in this dissertation. Mengyin and Pingyi volcanic rocks, which located in the south parts of western Shandong are shoshonite geochemically. while volcanic rocks cropped out in other places are high-K calc-alkaline series. All these volcanic rocks enriched in LREE and LILE. depleted in HFSE, and show TNT(strong negative anomalies in Ta, Nb. Ti) patterns in spider diagrams which are common phenomena in arc-related volcanic rocks. The Sr-Nd-Pb isotopic systematics reveal that the volcanic rocks decrease gradually in 87Sr/86Sr, 206Pb/204Pb, 20SPb/204Pb and increase in TDM from south to north, suggesting the distinction of SCLM beneath Shandong in Mesozoic is more explicit in south-north trending than in east-west trending. The variable features of SCLM can be attributed to the subduction of Yangtze craton beneath Sino-Korean craton, and subsequent metasomatism of SCLM by partial melts of Yangtze lower crust in different extent.

都龙锡锌矿床锡石和锆石U-Pb年代学：滇东南白垩纪大规模花岗岩成岩-成矿事件

都龙锡锌矿床是我国最大的锡石硫化物矿床之一.由于缺少可靠的年代学数据,对该矿床的成因尚存在较大争议.本文报道了利用锡石和锆石U-Pb法,首次获得的都龙锡锌矿床及相关的燕山晚期老君山花岗岩的年龄.其中,锡石TIMS法^206Pb/^238U年龄加权平均值为79.8±3.2Ma（MSWD=3.16）,^238U/^204Pb-^206Pb/^204Pb等时线年龄为82.0±9.6Ma（MSWD=4.81）;隐伏花岗岩的锆石SHRIMP法^206Pb/^238U年龄加权平均值为92.9±1.9Ma（N=10,MSWD=0.71）,花岗斑岩的锆石SHRIMP法^206Pb/^238U年龄加权平均值为86.9±1.4Ma（N=9,MSWD=3.70）,表明锡（铜）矿化主要与晚白垩世岩浆热液活动有关.结合个旧、白牛厂两个超大型矿床和相关花岗岩体的年代学资料,指示滇东南地区于白垩纪存在以锡矿化为特色的大规模花岗岩成岩-成矿事件,可能与晚中生代以来华南地块岩石圈伸展有关.

胶北晚中生代煌斑岩的岩石地球化学特征及其成因研究

胶北煌斑岩分别采自龙口、烟台和威海地区，包括拉辉煌斑岩、斜闪正煌岩和角闪煌斑岩，煌斑岩K—Ar全岩年龄变化于89．3～169．5Ma，为晚中生代岩浆活动的产物。在岩石化学组成上，SiO2=42．02％～54．95％，以钙碱性系列为主．岩石以富集大离子亲石元素（LILE）（Ba，U，K，Th）和LREE，亏损高场强元素（HFSE）（Nb，Ta和Ti）为特征，Mg^#=33．9～53．9，Eu／Eu^＊=0．71～0．89，^87Sr／^86Sr初始比值0．707642～0．709791，εNd（t）为-17．6～-10．4，^206Pb／^204Pb=37．588～38．431，^207Pb／^204Pb=15．423～15．531，^206Pb／^204Pb=17．204～18．179。表明煌斑岩源自俯冲陆壳（扬子下地壳）在地幔源区发生交代作用时形成的富集型地幔的部分熔融体．考虑到煌斑岩具有大陆边缘弧玄武岩的特征，我们认为煌斑岩在成因上同样与古大洋板块的俯冲作用有关，为碰撞后弧岩浆作用形成的脉岩。

鲁西晚中生代基性脉岩的成因和源区性质：岩石学和地球化学

本文从岩石学和地球化学方面对鲁西地区淄博盆地几个岩区的基性脉岩的成因和源区性质进行了探讨。脉岩的K-Ar年龄(72．2～116．3 Ma)表明其为晚中生代(白垩纪)岩浆作用的产物。主量元素显示该脉岩总体属钙碱性系列。微量元素特征表明脉岩为交代富集地幔部分熔融作用的产物，成岩过程可能同时经历了橄榄石、单斜辉石、Ti-Fe氧化物以及少量斜长石的分离结晶作用。Pb同位素组成：^208Pb／^204Pb=36．308～38．329；^207Pb／^204Pb=15．170～15．632；^206Pb／^204Pb=16．658～18．470，可以和下地壳组成相比，暗示成岩过程中存在大量下地壳物质的参与。岩浆在构造上受控于燕山造山带坍塌和沂沭断裂带(郯庐断裂山东段)的活动(左行平移和伸展)，但在上升侵位过程中没有遭受地壳物质的混染，且具有大陆边缘弧玄武岩的特性。这暗示岩浆早期鲁西地区存在古大洋板块(苏-鲁洋)的俯冲作用(即古俯冲作用)。