Responses of Estuarine Bacterioplankton,Phytoplankton and Zooplankton to Dissolved Organic Carbon (DOC) and Inorganic Nutrient Additions

The response of planktonic bacteria and phytoplankton to various additions of dissolved organic carbon (DOC) as glucose, with and without inorganic nutrients (nitrogen and phosphorus), was tested in the upper to mid Hunter Estuary, Australia. In situ microcosms (1.25 L) were performed at two sites with varying salinities over three seasons. Analysis of variance showed a significant difference among control and treatments for all seasons for the bacterial, dissolved oxygen and chlorophyll a responses (P < 0.05). A significant interaction between treatment and site was found in autumn for dissolved oxygen, autumn and spring for bacterial and spring for chlorophyll a responses. At both sites for each season, and on nearly all occasions, bacterial surface area was enhanced by DOC addition as indicated by both increased bacterial abundance and dissolved oxygen utilisation. DOC in combination with inorganic nutrients sometimes further enhanced the bacterial response compared to DOC alone. Inorganic nutrients alone did not enhance growth of the heterotrophic bacterioplankton. Addition of DOC alone led to decreased chlorophyll a relative to the control, probably due to competition for limited inorganic nutrients with the bacterioplankton DOC non-limiting conditions. Results suggest that the heterotrophic community was limited by DOC at both sites and across seasons. An experiment with a larger volume (70 L), performed over a longer time, compared a control with DOC addition. Increased bacterial biomass as a result of DOC addition occurred at day 2. Chlorophyll a did not significantly differ between treatments. An increase in zooplankton density was recorded in the DOC treatment relative to the control at day 10. This study supports the contention that increased DOC delivery with river inflows through environmental flow allocations will stimulate heterotrophic bacterioplankton production in the upper Hunter Estuary.     

Detrital zircon evidence for Hf isotopic evolution of granitoid crust and continental growth

We have determined U-Pb ages, trace element abundances and Hf isotopic compositions of approximately 1000 detrital zircon grains from the Mississippi, Congo, Yangtze and Amazon Rivers. The U-Pb isotopic data reveal the lack of >3.3 Ga zircons in the river sands, and distinct peaks at 2.7-2.5, 2.2-1.9, 1.7-1.6, 1.2-1.0, 0.9-0.4, and <0.3 Ga in the accumulated age distribution. These peaks correspond well with the timing of supercontinent assembly. The Hf isotopic data indicate that many zircons, even those having Archean U-Pb ages, crystallized from magmas involving an older crustal component, suggesting that granitoid magmatism has been the primary agent of differentiation of the continental crust since the Archean era. We calculated Hf isotopic model ages for the zircons to estimate the mean mantle-extraction ages of their source materials. The oldest zircon Hf model ages of about 3.7 Ga for the river sands suggest that some crust generation had taken place by 3.7 Ga, and that it was subsequently reworked into <3.3 Ga granitoid continental crust. The accumulated model age distribution shows peaks at 3.3-3.0, 2.9-2.4, and 2.0-0.9 Ga.The striking attribute of our new data set is the non-uniformitarian secular change in Hf isotopes of granitoid crusts; Hf isotopic compositions of granitoid crusts deviate from the mantle evolution line from about 3.3 to 2.0 Ga, the deviation declines between 2.0 and 1.3 Ga and again increases afterwards. Consideration of mantle-crust mixing models for granitoid genesis suggests that the noted isotopic trends are best explained if the rate of crust generation globally increased in two stages at around (or before) 3.3 and 1.3 Ga, whereas crustal differentiation was important in the evolution of the continental crust at 2.3-2.2 Ga and after 0.6 Ga. Reconciling the isotopic secular change in granitoid crust with that in sedimentary rocks suggests that sedimentary recycling has essentially taken place in continental settings rather than active margin settings and that the sedimentary mass significantly grew through addition of first-cycle sediments from young igneous basements, until after ∼1.3 Ga when sedimentary recycling became the dominant feature of sedimentary evolution. These findings, coupled with the lack of zircons older than 3.3 Ga in river sands, imply the emergence of large-scale continents at about 3.3 Ga with further rapid growth at around 1.3 Ga. This resulted in the major growth of the sedimentary mass between 3.3 and 1.3 Ga and the predominance of its cannibalistic recycling later.     

Grain-scale iron isotopic distribution of pyrite from Precambrian shallow marine carbonate revealed by a femtosecond laser ablation multicollector ICP-MS technique: Possible proxy for the redox state of ancient seawater

The redox state of Precambrian shallow seas has been linked with material cycle and evolution of the photosynthesis-based ecosystem. Iron is a redox-sensitive element and exists as a soluble Fe(II) species or insoluble Fe(III) species on Earth’s surface. Previous studies have shown that the iron isotopic ratio of marine sedimentary minerals is useful for understanding the ocean redox state, although the redox state of the Archean shallow sea is poorly known. This is partly because the conventional bulk isotope analytical technique has often been used, wherein the iron isotopic record may be dampened by the presence of isotopically different iron-bearing minerals within the same sample. Here we report a microscale iron isotopic ratio of individual pyrite grains in shallow marine stromatolitic carbonates over geological time using a newly developed, near-infrared femtosecond laser ablation multicollector ICP-MS technique (NIR-fs-LA-MC-ICP-MS).We have determined that the grain-scale iron isotopic distribution of pyrite from coeval samples shows a bimodal (2.7 and 2.3 Ga) or unimodal pattern (2.9, 2.6, and 0.7 Ga). In particular, pyrite from the 2.7 Ga Fortescue Group shows a unique bimodal distribution with highly positive (+1.0‰ defined as Type 1) and negative δ⁵⁶Fe values (−1.8‰ defined as Type 2). Type 1 and 2 pyrites occasionally occur within different siliceous layers in the same rock specimen. Layer-scale iron isotopic heterogeneity indicates that the iron isotopic ratios of the two types of pyrite are not homogenized by diagenesis after deposition. Some cubic pyrites have a core with a positive δ⁵⁶Fe value (1‰) and a rim with a crustal δ⁵⁶Fe value (0‰). The observed isotopic zoning suggests that the positive δ⁵⁶Fe value is a primary signature at the time of stromatolite formation, while secondary pyrite precipitated during diagenesis.The positive δ⁵⁶Fe value of Type 1 and the large iron isotopic difference between Type 1 and 2 (2.8‰.) suggest partial Fe(II) oxidation in the 2.7-Ga shallow sea, i.e., pyritization of ⁵⁶Fe-enriched ferric oxyhydroxide (Type 1) and ⁵⁶Fe depleted Fe²⁺aq in seawater (Type 2). Type 2 pyrite was probably not produced by microbial iron redox cycling during diagenesis because this scenario requires a higher abundance of pyrite with δ⁵⁶Fe of 0‰ than of −1.8‰. Consequently, the degree of Fe(II) oxidation in the 2.7-Ga shallow sea can be estimated by a Fe²⁺aq steady-state model. The model calculation shows that half the Fe²⁺aq influx was oxidized in the seawater. This implies that O₂ produced by photosynthesis would have been completely consumed by oxidation of the Fe²⁺aq influx. Grain-scale iron isotopic distribution of pyrite could be a useful index for reconstructing the redox state of the Archean shallow sea.     

Redox history of the Three Gorges region during the Ediacaran and Early Cambrian as indicated by the Fe isotope

The Ediacaran-Cambrian transition is characterized by numerous events such as the emergence of large multi-cellular metazoans and surface environmental disturbances.Based on geological evidence,it has been proposed that this transition coincided with the increase in the atmospheric oxygen level that was key to the evolution of life.Even though ancient redox conditions can be inferred from the composition of sedimentary iron mineral species,this method is not necessarily applicable to all rocks.In the Earth system,the cycling of iron is of considerable interest owing to its sensitivity to redox conditions.Information regarding the paleo-oceanic iron cycle is revealed in the iron isotopic composition of ironbearing minerals.Unfortunately,only limited iron isotopic data exists for Ediacaran-to Cambrianperiod oceans.To circumvent this deficiency,we drilled a fossiliferous Ediacaran to Early Cambrian sedimentary succession in the Three Gorges region,South China.We analyzed the iron isotope ratios(δ~(56/54)Fe)of pyrite grains in the drill cores using laser ablation multi collector inductively coupled plasma mass spectrometry.The results demonstrate large variations inδ~(56/54)Fe,from-1.6 to 1.6‰,and positive iron isotope ratios are observed in many successions.The presence of positiveδ~(56/54)Fe in pyrite indicates that the ferrous iron in the seawater was partially oxidized,suggesting that seawater at Three Gorges was ferruginous during the Ediacaran and Early Cambrian periods.However,aggregated pyrite grains in organic carbon-rich black shales at Member 4 of the Doushantuo Formation and the base of the Shuijingtuo Formation yield near-zeroδ~(56/54)Fe values;this suggests that the ocean was transiently dominated by sulfidic conditions during these periods.Notably negativeδ~(56/54)Fe values,lower than-1‰,can be interpreted as a signature of DIR.The DIR also might contribute in part to the re-mineralization of organic matter during the largest negative carbon isotope anomaly in the Ediacaran.     

Indicator of paleosalinity: Sedimentary sulfur and organic carbon in the Jurassic–Cretaceous Tetori Group,central Japan

A simple geochemical technique using the ratio of total sulfur (TS) to total organic carbon (TOC) was successfully used to reconstruct paleoenvironments in the Jurassic–Cretaceous Tetori Group, central Japan. The TS to TOC ratio is often employed as an effective parameter to separate modern marine or brackish sediments from freshwater deposits. To test the TS/TOC method for paleoenvironmental interpretation of the Tetori Group, we first analyzed TS/TOC for samples for which depositional conditions (i.e. marine, brackish or freshwater) had been recognized paleontologically. The results indicate that the method can effectively separate sedimentary rocks deposited under freshwater from marine and brackish settings. Once we had established the effectiveness of this method, we applied it to three sections of the Tetori Group, central Japan. Stratigraphic fluctuations in TS/TOC values revealed episodic incursions of marine or brackish conditions in the dominantly freshwater depositional sequence in the middle of the Jobu Formation of the Itoshiro Subgroup at the Izumi section, Fukui Prefecture. The same paleoenvironment is also suggested to occur at the top of the Tetori Group in the Tateyama section, Toyama Prefecture. This research provides important information to paleogeographers who currently lack evidence from facies fossils to indicate if the uppermost part of the Tetori Group represents marine or brackish settings. A chemostratigraphy of TS/TOC parameters potentially could provide a correlation among Jurassic–Cretaceous sequences along continental margins over East Asia.     

Occurrence and chemical composition of the Eoarchean carbonate rocks of the Nulliak supracrustal rocks in the Saglek Block of northeastern Labrador,Canada

The Eoarchean Nulliak supracrustal rocks in the Saglek Block of northeastern Labrador, Canada, contain some of the world's oldest carbonate rocks. This work attempted to reveal the origin of the carbonate rocks and estimate the surface environmental conditions of the early Earth based on their occurrence and geochemistry. They occur together with mafic and ultramafic rocks in Pangertok Inlet and St. John's Harbour South, whereas they are interlayered with pelitic rock layers with quartzofeldspathic mineral assemblages in St. John's Harbour East and Big Island. The geological occurrence suggests that the formers were formed around hydrothermal fields, whereas the latters were deposited near a continental margin. Some carbonate rocks have high SiO₂, Al₂O₃, and Zr contents, indicating that the silicification and involvement of detrital materials influenced their composition; thus, pure carbonate rocks were selected using a combined filter of the SiO₂, TiO_2, Al₂O₃, Zr, and Ba contents. The selected carbonate rocks have positive La, Eu, Gd, Y, U, Pb, and Sr anomalies, negative Nb, Zr, and Hf anomalies, and relatively small enrichment in heavy rare earth elements (HREEs). The La and Y anomalies suggest that they originated from chemical sediments precipitated from seawater. On the other hand, the small HREE-enrichment suggests that REEs were mainly dissolved as REE-carbonate complexes in seawater or that the riverine influxes were dominated by the detritus of Eoarchean continental crusts, presumably composed of HREE-depleted TTG. The U anomaly suggests that uranium was more dissolved than Th as U-bearing carbonate complexes in seawater. The Nulliak carbonate rocks also show a positive correlation between Y and Eu anomaly values, suggesting that the precipitation of iron-oxyhydroxide causing the Y anomaly was more significant near the hydrothermal fields than the continental margin, consistent with an alkaline hydrothermal model.     

Chemostratigraphy of the Ediacaran basinal setting on the Yangtze platform,South China: Oceanographic and diagenetic aspects of the carbon isotopic depth gradient

The Ediacaran Yangtze platform in South China, which represents depositional settings ranging from coastal to basinal, provides valuable information for understanding climate changes and animal evolution during the Ediacaran Period. Although the shallower settings have been investigated, research on the basinal sections has been limited. This has hampered efforts to establish stratigraphic correlations and understand the oceanographic setting of the Yangtze platform. In this paper, the chemostratigraphy of a basinal section at Fengtan, Hunan Province, is reported based on analyses of stable carbon isotope profiles in carbonates (δ¹³C_carb), organic matter (δ¹³C_org), total organic carbon, ⁸⁷Sr/⁸⁶Sr ratios, and Mn, Rb, and Sr concentrations. The basinal section of the Doushantuo Formation, which is represented at Fengtan, provides data supporting regional correlations and oceanography. Three intervals in the Doushantuo Formation are correlated with the Three Gorges: (i) a negative δ¹³C_carb anomaly with stable δ¹³C_org values and altered ⁸⁷Sr/⁸⁶Sr ratios in the lower section can be correlated to the boundary between Doushantuo Members 2 and 3 (Interval A); (ii) a relatively high δ¹³C_carb anomaly with unaltered ⁸⁷Sr/⁸⁶Sr ratios (up to 0.7086) in the middle section corresponding to the lower part of Doushantuo Member 3 (Interval B); and (iii) a negative δ¹³C_carb anomaly with lowered δ values in the upper section can be correlated to the long interval of negative δ¹³C_carb (Interval C). The Gaskiers glaciation is likely represented in Interval A, and Interval C corresponds to the Shuram excursion reported for other Ediacaran localities. Our correlations confirm the depth gradient of δ¹³C_carb in the Yangtze platform and imply that reductive conditions prevailed in the basinal section from the Early to Middle Ediacaran. Under such conditions, anaerobic degradation of organic carbon or methane perturbed the inorganic carbon isotopic compositions and was at least partly responsible for the depth gradient of δ¹³C_carb.     

Zircon U–Pb ages from tuff beds of the upper Mesozoic Tetori Group in the Shokawa district,Gifu Prefecture,central Japan†

Abstract The upper Mesozoic Tetori Group contains numerous fossils of plants and marine and non‐marine animals. The group has the potential to provide key information to improve our understanding of the Middle Jurassic to Early Cretaceous biota of East Asia. However, the depositional age of the Tetori Group remains uncertain, and without good age constraints, accurate correlation with other areas is very difficult. As a first step in obtaining reliable ages for the formations within the Tetori Group, we used laser ablation‐inductively coupled plasma–mass spectrometry to measure the U–Pb ages of zircons collected from tuff beds in the Shokawa district, Takayama City, Gifu Prefecture, central Japan. The youngest reliable U–Pb ages from the tuff beds of the Ushimaru, Mitarai and Okurodani Formations are 130.2 ± 1.7, 129.8 ± 1.0 and 117.5 ± 0.7 Ma, respectively (errors represent 2 SE). These results indicate that the entire Tetori Group in the Shokawa district, which was previously believed to be correlated to the Upper Jurassic to Lower Cretaceous, is in fact correlated to the Lower Cretaceous. The maximum ages of the Ushimaru, Mitarai and Okurodani Formations are late Hauterivian to Barremian, late Hauterivian to Barremian and Barremian to Aptian, respectively.     

Geological significance of rare earth elements in Japanese geosynclinal basalts

Rare earth elements (REE), Ba, Sr as well as major elements in 47 pre-Cenozoic geosynclinal volcanics in Japan have been determined. The types of chondrite-normalized REE patterns can be classified into two large groups viz. log-linear REE pattern group and convex REE pattern group. Each group thus classified is also closely related to major element features. Although the REE pattern of the latter group is observed in the island arc tholeiite as well as abyssal tholeiite, the relative content of Ba to La indicates that the Japanese geosynclinal volcanics of this group are more akin to those of abyssal tholeiites than are the island arc ones. Two distinct types of REE fractionation are found in the volcanics of the Japanese geosyncline. The geographical distribution of two groups of the geosynclinal volcanics is different from that of the Cenozoic volcanics in Japan, and the petrochemical features of volcanics from northeast Japan can be distinguished from those of southwest Japan. By analogy with the current knowledge concerning a close relation between the tectonic settings and the geochemical features of the present-day volcanics, the geosynclinal basalts in question are inferred to have been formed during a tensional tectonic movement and have erupted along a local rift zone like the marginal seas and inter-arc basins in the Western Pacific Ocean or along part of a global rift system such as the Red Sea Trough.     

Geochemistry and petrogenesis of carbonatites from South Nam Xe,Lai Chau area,northwest Vietnam

This paper presents a study of the petrography, mineral chemistry, geochemistry, and Sr–Nd–Pb–C–O isotope systematics of carbonatite dykes and associated rocks from the northeastern part of the Song Da intracontinental rift in South Nam Xe (northwest Vietnam) aimed at constraining the origin of the carbonatite magmas. The carbonatites are characterized by SiO₂ < 12.18 wt.% and by wide ranges in FeO, MgO and CaO content that define them as calciocarbonatite and ferrocarbonatite. On U–Th–Pb isochron diagrams, whole rocks and mineral separates from the ferrocarbonatites form linear arrays corresponding to ages of 30.2–31.6 Ma (Rupelian, Oligocene). The South Nam Xe carbonatites are extremely enriched in Sr, Ba, and light rare earth elements (LREE), and depleted in high field strength elements (HFSE) (e.g. Ti, Nb, Ta, Zr and Hf). The age–corrected Sr–Nd–Pb isotope ratios and C isotope data are relatively uniform (⁸⁷Sr/⁸⁶Sr_(t) = 0.708193–0.708349; ¹⁴³Nd/¹⁴⁴Nd_(t) = 0.512250–0.512267; ε_Nd(t) = ?6.46 to ?6.80; ²⁰⁶Pb/²⁰⁴Pb_(t) = 18.26–18.79; ²⁰⁷Pb/²⁰⁴Pb_(t) = 15.62–15.64; ²⁰⁸Pb/²⁰⁴Pb_(t) = 38.80–39.38; δ¹³C_V-PDB = –2.7?‰ to ?4.1?‰). These isotopic compositions indicate source contamination that occurred before the production of the carbonatite magmas, and did not change noticeably during or after emplacement. The variation in oxygen isotopes is consistent with the change in mineral compositions and trace element abundances: the lower δ¹⁸O values (9.1–11.0?‰) coupled with Sr-rich, Mn-poor calcite, and igneous textures such as triple junctions among calcite grain boundaries, define a magmatic origin. However, the elevated δ¹⁸O values of the ferrocarbonatites (12.0–13.3?‰) coupled with a volatile-bearing mineral assemblages (including REE fluorcarbonates, sulfates, sulfides and fluorite) may be due to interaction with meteoric water during low-temperature alteration. High δ¹³C values and Sr–Pb ratios, and low Rb/Sr (0.00014–0.00301), Sm/Nd (0.089–0.141) and ¹⁴³Nd/¹⁴⁴Nd ratios, coupled with very high Sr-Nd concentrations, suggest the involvement of an enriched mantle component, which probably resulted from metasomatism due to the migration of subducted material. Because of the lack of tectonic data and the limited number of samples studied, this conclusion is still ambiguous and requires further study.