Stable carbon isotope distribution of particulate organic matter in the ocean: a model study

The stable carbon isotopic composition of particulate organic matter in the ocean, δ¹³C_POC, shows characteristic spatial variations with high values in low latitudes and low values in high latitudes. The lowest δ¹³C_POC values (−32‰ to −35‰) have been reported in the Southern Ocean, whereas in arctic and subarctic regions δ¹³C_POC values do not drop below −27‰. This interhemispheric asymmetry is still unexplained. Global gradients in δ¹³C_POC are much greater than in δ¹³C_DIC, suggesting that variations in isotopic fractionation during organic matter production are primarily responsible for the observed range in δ¹³C_POC. Understanding the factors that control isotope variability is a prerequisite when applying δ¹³C_POC to the study of marine carbon biogeochemistry. The present model study attempts to reproduce the δ¹³C_POC distribution pattern in the ocean. The three-dimensional (3D) Hamburg Model of the Oceanic Carbon Cycle version 3.1 (HAMOCC3.1) was combined with two different parametrizations of the biological fractionation of stable carbon isotopes. In the first parametrization, it is assumed that the isotopic fractionation between CO₂ in seawater and the organic material produced by algae, _P, is a function of the ambient CO₂ concentration. The two parameters of this function are derived from observations and are not based on an assumption of any specific mechanism. Thus, this parametrization is purely empirical. The second parametrization is based on fractionation models for microalgae. It is supported by several laboratory experiments. Here the fractionation, _P, depends on the CO₂ concentration in seawater and on the (instantaneous) growth rates, μ_i, of the phytoplankton. In the Atlantic Ocean, where most field data are available, both parametrizations reproduce the latitudinal variability of the mean δ¹³C_POC distribution. The interhemispheric asymmetry of δ¹³C_POC can mostly be attributed to the interhemispheric asymmetry of CO₂ concentration in the water. However, the strong seasonal variations of δ¹³C_POC as reported by several authors, can only be explained by a growth rate-dependent fractionation, which reflects variations in the cellular carbon demand.     

Characteristics and origin of carbon isotopes of n-alkanes in crude oils from the western Pearl River Mouth Basin,South China sea

The quantitative characterization of carbon isotopes of n-alkanes is commonly carried out in organic geochemical studies. Possible controls on carbon isotopes include source organic matter, maturity, fractionation during oil expulsion and migration, and the mixing of different oils. In this study of the origin of crude oils in the western Pearl River Mouth Basin, the influences of all of these factors have been considered in reaching a conclusion. Carbon isotopes of n-alkanes in the crude oils, and the extracts of the two effective source rocks (the Wenchang and Enping formations) in the basin, exhibit clear differences. The Wenchang source rocks have heavy δ¹³C values that remain almost constant or become slightly heavier with increasing carbon number. The Enping source rocks have light δ¹³C values that become lighter with increasing carbon number. Two groups of oils in this area were identified based on the carbon isotopes of the n-alkanes; groupIoils are similar to extracts of the Wenchang source rocks. However, the groupIIoils are different from both the Wenchang and Enping source rocks and the carbon isotopic profiles of their n-alkanes exhibit a “V” feature with increasing carbon number. The results of artificial thermal maturation experiments indicate that, from the early stage to the peak stage of oil generation (with EasyRo between 0.64% and 1.02%), the δ¹³C values of n-alkanes in the pyrolysis oils become heavier by about 3‰ with increasing thermal maturity, but the shape of the carbon isotopic profiles are not significantly changed. Calculated δ¹³C values of n-alkanes in “mixed” artificial pyrolysis oils indicate that the mixture of oils generated from the same source rocks with different maturities could not change the carbon isotopic profile of the n-alkanes, however, a mixing of the Wenchang and Enping oils could give the “V” feature in the profiles, similar to the groupIIoils in this area. The groupIIoils appear to be mixed Wenchang and Enping oils, the latter being the dominant component in the mixture. We conclude that the source organic matter and the degree of mixing are the main factors controlling the carbon isotopic characteristics of n-alkanes in crude oils in the western Pearl River Mouth Basin.     

Trophic significance of the kelp Laminaria digitata (Lamour.) for the associated food web: a between-sites comparison

This study aimed at establishing the trophic significance of the kelp Laminaria digitata for consumers inhabiting two rocky shores of Northern Brittany (France), displaying contrasted ecological conditions. The general trophic structure did not vary between these two sites, with a wide diversity of filter-feeders and predators, and only 14% of the species sampled belonging to the grazers' trophic group. The diversity of food sources fueling the food web appeared also similar. The food webs comprised four trophic levels and the prevalence of omnivory appeared relatively low compared to previous studies in the same area. Conversely, to the food web structure, which did not differ, the biochemical composition of L. digitata differed between the two sites, and was correlated to a larger diversity of grazers feeding on this kelp in sheltered conditions. This indicated that the spatial variability occurring in the nutritive value of L. digitata is likely to deeply affect the functioning of kelp-associated food webs. The contribution of L. digitata-derived organic matter to the diet of filter-feeders inhabiting these two environments was assessed using the mixing model Isosource, which showed the higher contribution of kelp matter in sheltered conditions. These results highlight the spatial variability that may occur in the functioning of kelp-associated food webs. Moreover, this suggests that hydrodynamics is likely to control the availability of kelp-derived organic matter to local filter-feeders, probably through an increase of detritus export in exposed areas.     

Oscillatory zoning in garnet from the Willsboro Wollastonite Skarn, Adirondack Mts, New York: a record of shallow hydrothermal processes preserved in a granulite facies terrane

Oscillatory zoning in low δ¹⁸O skarn garnet from the Willsboro wollastonite deposit, NE Adirondack Mts, NY, USA, preserves a record of the temporal evolution of mixing hydrothermal fluids from different sources. Garnet with oscillatory zoning are large (1–3 cm diameter) euhedral crystals that grew in formerly fluid filled cavities. They contain millimetre‐scale oscillatory zoning of varying grossular–andradite composition (X_Adr = 0.13–0.36). The δ¹⁸O values of the garnet zones vary from 0.80 to 6.26‰ VSMOW and correlate with X_Adr. The shape, pattern and number of garnet zones varies from crystal to crystal, as does the magnitude of the correlated chemistry changes, suggesting fluid system variability, temporal and/or spatial, over the time of garnet growth. The zones of correlated Fe content and δ¹⁸O indicate that a high Fe³⁺/Al, high δ¹⁸O fluid mixed with a lower Fe³⁺/Al and δ¹⁸O fluid. The high δ¹⁸O, Fe enriched fluids were likely magmatic fluids expelled from crystallizing anorthosite. The low δ¹⁸O fluids were meteoric in origin. These are the first skarn garnet with oscillatory zoning reported from granulite facies rocks. Geochronologic, stable isotope, petrologic and field evidence indicates that the Adirondacks are a polymetamorphic terrane, where localized contact metamorphism around shallowly intruded anorthosite was followed by a regional granulite facies overprint. The growth of these garnet in equilibrium with meteoric and magmatic fluids indicates an origin in the shallow contact aureole of the anorthosite prior to regional metamorphism. The zoning was preserved due to the slow diffusion of oxygen and cations in the large garnet and protection from deformation and recrystallization in zones of low strain in thick, rigid, garnetite layers. The garnet provide new information about the hydrothermal system adjacent to the shallowly intruded massif anorthosite that predates regional metamorphism in this geologically complex, polymetamorphic terrane.     

Organic matter origin and distribution in suspended particulate materials and surficial sediments from the western Adriatic Sea (Italy)

In this study, organic carbon (OC), total nitrogen (TN), stable carbon isotopic (δ¹³C_OC) and CuO reaction product compositions were used to identify the sources of organic matter (OM) and to quantify the relative importance of allochthonous and autochthonous contributions to the western Adriatic Sea, Italy. Suspended particulate material (195 samples) and surficial sediments (0–1 cm, 70 samples) from shallow cross-shelf transects were collected in February and May 2003, respectively. Vertical water column profiles were acquired along the same transects. Data include depth, potential temperature, salinity, density and chlorophyll fluorimetry.Along the western Adriatic shelf in the near-shore region, the phytoplankton growth was influenced by dynamics of the buoyant plumes from the Po and Appennine rivers. A small amount of very fine terrigenous material remained suspended within the coastal current and was exported southward along the shelf to the slope. High variability in the bulk composition was detected in the Po prodelta surficial sediments, whereas the western Adriatic shelf, although a larger area, exhibited a narrower range of values.A significant decoupling was observed between suspended particles in the water column and surficial deposits. The organic material collected in the water column was compositionally heterogeneous, with contributions from marine phytoplankton, riverine–estuarine phytoplankton and soil-derived OM. Frequent physical reworking of surficial sediments likely leads to the efficient oxidation of marine OC, resulting in the observed accumulation and preservation of refractory soil-derived OC delivered by the Po and Appennine rivers.     

稳定同位素方法在海洋N_2O研究中应用展望

氧化亚氮(N2O)是大气中重要和微量的温室气体,且在平流层N2O形成NO自由基与O3发生反应破坏臭氧层.海洋是大气中N2O净源,但由于海洋中生物化学过程的复杂性,有关N2O形成机制至今是人们研究的重点和难点.应用稳定同位素分馏原理对海洋中N2O形成机制的研究,区分海洋中通过硝化和反硝化过程不同途径产生的N2O过程,为深入研究海洋中N2O循环、估算将来大气中N2O浓度变化提供有用工具.     

Identification of Pb sources in Yellow Sea sediments using stable Pb isotope ratios

Rapid economic developments in East Asian countries have inevitably resulted in environmental degradation in the surrounding seas, and concern for both the environment and protection from pollutants is increasing. Identification of sources of contaminants is essential to environmental pollution management. In this study, the provenance of anthropogenic lead (Pb), a major pollutant of Yellow Sea sediments, was determined for river mouth sediments, including those of the Changjiang, Huanghe, Han, and Geum Rivers, and for age-determined shelf core sediments through the measurement of Pb isotope ratios in the HCl-leached fraction using multi-collector inductively coupled plasma-mass spectrometry (MC ICP/MS). Anthropogenic Pb has accumulated in shelf core sediments since 1910, and its isotope ratios were estimated as 0.863–0.866 and 2.119–2.125 for ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb, respectively, from the mixing relationships of the two endmembers. River mouth sediments exhibited enough distinction in anthropogenic Pb isotope ratios to be discriminated: 0.874 (2.144) in the Huanghe, 0.856 (2.129) in the Han, 0.857 (2.122) in the Geum, and 0.854 (2.101) in the Changjiang for ²⁰⁷Pb/²⁰⁶Pb (²⁰⁸Pb/²⁰⁶Pb), respectively. Although isotope ratios of geogenic Pb in sediments dating before 1910 showed narrow ranges (0.842–0.845 and 2.088–2.100 for ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb, respectively), distinct isotope ratios in each core permitted source identification of sediments in the Yellow Sea based on geographic locations and the geogenic Pb of each river. By comparing the isotope ratios of the estimated anthropogenic Pb to source-related materials, the provenances of anthropogenic Pb in Chinese river sediments were presumed to be Chinese coal or ore, which is also a major source of atmospheric particulate Pb. The anthropogenic Pb in the shelf core sediments in the northern Yellow Sea originated from northern Chinese cities such as Beijing and Tianjin through atmospheric pathways. Pb isotope ratios indicated that Pb in Korean river sediments was characteristic of local Korean ores.     

胶州湾沉积物中有机硫来源及成因机制的研究

有机硫是海洋沉积物中重要的硫形态,其中成岩有机硫对有机质保存和微量元素形态具有重要影响。利用化学提取及硫稳定同位素研究了胶州湾沉积物中碱可提取的腐殖酸硫(HA-S)、富里酸硫(FA-S)以及铬不可还原有机硫(non-CROS)的垂直分布、来源及形成机制。结果表明,non-CROS、HA-S以及FA-S的含量范围分别为19.1~52.6、3.35~7.82和27.3~38.6μmol/g,均处于其他许多近海沉积物中含量的低值区,且3者均为海洋生物有机硫和成岩有机硫的混合物。HA-S和nonCROS以海洋生物有机硫为主,其份数分别为65%~68%和67%~77%,而FA-S则以成岩有机硫为主(54%~73%)。相对于生物有机硫,成岩有机硫更易被碱和酸性Cr(Ⅱ)溶液提取,因此腐殖质硫和non-CROS都不能全面反映沉积物中有机硫的组成和来源。黄铁矿和腐殖质中成岩有机硫含量随深度的同步增加表明黄铁矿形成并未明显地竞争性抑制有机质硫化。     

冲绳海槽有孔虫壳体的微量元素Sr,Nd同位素地球化学

钙质生物壳的微量元素组合和Sr,Nd同位素组成是识别海底混合源沉积物中生物源物质相对贡献的重要参数.冲绳海槽有孔虫壳体强烈富集Sr,P,Mn和Ba,富集Li,U,Th,Sc,Co,Pb,Zn,Cr,Rb,Y,Sb和轻稀土元素,弱富集V,Ga,Zr,Nb,Cd和中稀土元素,相对贫Ge,Mo,In,Sn,Cs,Hf,Ta,W,Tl,Bi和重稀土元素,海水中微量元素的背景含量和生物活动对微量元素的选择性吸收是有孔虫壳体中微量元素发生富集和贫化的主要机制,冲绳海槽有孔虫壳体的稀土元素配分模式与海水和太平洋有孔虫的有明显差异,表现出中稀土元素相对富集,并具有微弱的负Ce异常.有孔虫壳体的Sr,Nd同位素比值也与大洋海水不同,分别为0.709769和0.512162,前者略高于大洋海水,后者略低于大洋海水,表明冲绳海槽海水明显受大陆河水影响.