On the stable carbon and oxygen isotopic composition of some shallow water,ahermatypic, scleractinian coral skeletons

The δC¹³ and δO¹⁸ values of skeletons of shallow water, ahermatypic scleractinian corals from Jamaica show an excellent correlation over a wide range of isotopic composition. Within individual specimens there are large differences in the isotopic composition of separate skeletal elements. Some of these ahermatypes are enriched in O¹⁸ relative to equilibrium precipitates of calcium carbonate from Jamaican sea water. Therefore our data do not support a two-reservoir mixing model for calcification if one of these reservoirs consists of dissolved marine (inorganic) bicarbonate. As some of these ahermatypic species are enriched in both C¹³ and O¹⁸ relative to hermatypic corals from the same reefs, calcification models based on withdrawal of metabolic CO₂ by photosynthesizing zooxanthellae must also be modified.     

The build up of the isotopic signal in skeletons of the stony coral Porites lutea

The build up of the isotopic signal in corals was followed by sampling the newly formed skeleton at a monthly resolution for a period of two years in order to establish the interrelations between the calcification processes and the skeletal isotopic composition. We deployed two underwater sampling schemes, which provide a monitor of the changes in water temperature and δ¹⁸O and in the corresponding newly accreted skeleton of undisturbed Porites lutea colonies under natural conditions and four transplanted colonies, which maintained the genetic identity throughout the experiment. The results indicate that δ¹⁸O of the newly accreted skeleton does not correlate with ambient temperature although the seasonal temperature variability at the site (winter to summer) is in the order of 6 °C and δ¹⁸O of seawater is constant throughout the year. In contrast to the newly formed surface skeleton, the isotopic compositions of the deep and older parts of the skeleton show the predicted annual isotopic pattern with highly significant correlation between δ¹⁸O_s and SST. The transformation between temperature-independent to temperature-dependent isotopic signal occurs several months after the skeleton was formed at the surface. The position of the skeleton in relation to the open sea may generate the difference between δ¹⁸O_s of the surface skeleton and that of the skeleton previously accreted further down the tissue layer. Our data support the general model of a multi-step skeletogenesis process, where the temperature independent skeleton is entails the first step, the production of skeletal scaffold, and the environmental temperature signature is captured by the next two other steps: the thickening and the periodic abrupt uplift occurring at the depth of the tissue layer. However, re-examination and development of the current isotopic models for coral calcification are required in order to explain the observed different temperature dependency during the growth’s sequence.     

Annual fluctuation in the stable carbon isotope ratio of coral skeletons: The relative intensities of kinetic and metabolic isotope effects

Stable carbon and oxygen isotope measurements of biogenic carbonate provide information for reconstructing past oceanic environments. In particular, ¹⁸O/¹⁶O ratios correlate with the temperature and salinity of seawater and ¹³C/¹²C is a proxy for dissolved inorganic carbon in seawater and symbiont photosynthesis. Here, we report ¹³C/¹²C and ¹⁸O/¹⁶O values for skeletons of corals (genus Porites) with various growth rates. In faster-growing corals, ¹³C/¹²C and ¹⁸O/¹⁶O showed out-of-phase annual fluctuations. In slower-growing corals, the isotopes fluctuated in phase. We developed a simple vector notation to show two patterns of ¹³C/¹²C annual fluctuation, each with a different offset in relation to ¹⁸O/¹⁶O annual fluctuation. The phase offset between ¹³C/¹²C and ¹⁸O/¹⁶O annual fluctuations depends on the relative intensities of kinetic isotope effects on calcification and metabolic isotope effects such as photosynthesis. This model might improve our ability to infer past climate and oceanographic conditions from coral skeletons.     

The distribution and stable carbon isotopic composition of dissolved organic carbon in estuaries

The distributions of dissolved organic carbon (DOC) and the natural carbon isotope ratio of DOC (DO¹³C) in estuaries reflect the predominant sources and sinks of organic matter from both allochthonous and autochthonous origins. The traditional view is that DOC in land-margin ecosystems reflects mainly the mixing of land-derived and oceanic DOC. However, this view is not consistent with the bulk of our data from a survey of DOC and DO¹³C distributions in estuaries on the East and Gulf coasts of the USA. While it is accurate that the DOC in estuaries includes material derived from land and from the ocean, the distributions of DOC and DO¹³C in several estuaries reflect additional DOC inputs from estuarine phytoplankton and tidal marshes. Even when DOC concentrations were distributed conservatively, the isotopic composition of the DOC revealed the existence of a dynamic cycle of DOC input and removal in some systems.     

Preservation of organic matter in mound-forming coral skeletons

This study demonstrates that intracrystalline organic matter in coral skeletons is well preserved over century timescales. The extent of preservation of organic matter in coral skeletons was investigated by measuring total organic carbon (TOC), total hydrolyzable amino acid (THAA), chloropigment, and lipid concentrations in 0-300 year old annual growth bands from Montastraea annularis (Florida Keys) and Porites lutea (Red Sea). Organic matter intrinsic to the calcium carbonate mineral (intracrystalline) was analyzed separately from total skeletal organic matter. The Red Sea coral had less TOC (0.02-0.04 wt%) than the Florida Keys coral (0.04-0.11 wt%), but a higher percent of intracrystalline organic matter in all annual bands measured. Carbon in the form of THAA, most likely from mineral-precipitating proteins, contributed 30-45% of the TOC in both corals. Carbon in lipids represented about 3% of the TOC in the coral skeletons. Chlorophyll-a and b were present in annual bands where endolithic algae were present, but these compounds were minor contributors to TOC. The distribution of specific organic compounds showed that organic matter was well preserved throughout the time period sampled in both the total and intracrystalline pools. Variations in THAA were not correlated with TOC over time, suggesting that organic matter that is involved in biomineralization, like amino acids, may be deposited in response to different environmental factors than are other components of skeletal organic matter. Differences in the quantity and composition of organic matter between the two corals investigated here were assessed using principal components analysis and suggest that location, species and skeletal structure may all influence organic matter content and possibly the degree of physical protection of organic matter by the coral skeleton. Further, our study suggests that intracrystalline organic matter may be better protected from diagenesis than non-intracrystalline organic matter and may therefore be a more reliable source of organic matter for paleoceanographic studies than total skeletal organic matter.     

The stable isotopic composition (Cl/Cl) of dissolved chloride in rainwater

The stable isotopic composition of dissolved Cl^-${\text{Cl}}^{-}$ in rainwater was measured from a coastal and an interior location in eastern Canada. At the interior Bonner Lake, Ontario, site the δ³⁷Cl values of dissolved Cl^-${\text{Cl}}^{-}$ in precipitation ranged from −3.5‰ to −1.2‰ (SMOC) with an amount-weighted annual average of −2.3‰. At the coastal site, Bay D’Espoir, Newfoundland, δ³⁷Cl values of dissolved Cl^-${\text{Cl}}^{-}$ values ranged from −3.1‰ to 0.0‰ with an amount-weighted annual average of −1.3‰. These negative δ³⁷Cl values provide evidence that atmospheric HCl is ³⁷Cl depleted, presumably from acidification of sea-salt aerosols. Accordingly, dissolved Cl^-${\text{Cl}}^{-}$ in the headwaters of two montane rivers in Western Canada had similarly depleted δ³⁷Cl values. These results have implications to the interpretation of the isotopic compositions of dissolved Cl^-${\text{Cl}}^{-}$ in surface waters, formation fluids, and groundwaters.     

Deep-sea coral aragonite as a recorder for the neodymium isotopic composition of seawater

Deep-sea corals have been shown to be useful archives of rapid changes in ocean chemistry during the last glacial cycle. Their aragonitic skeleton can be absolutely dated by U-Th data, freeing radiocarbon to be used as a water-mass proxy. For certain species of deep-sea corals, the growth rate allows time resolution that is comparable to ice cores. An additional proxy is needed to exploit this opportunity and turn radiocarbon data into rates of ocean overturning in the past.Neodymium isotopes in seawater can serve as a quasi-conservative water-mass tracer and initial results indicate that deep-sea corals may be reliable archives of seawater Nd isotopes. Here we present a systematic study exploring Nd isotopes as a water-mass proxy in deep-sea coral aragonite. We investigated five different genera of modern deep-sea corals (Caryophyllia, Desmophyllum, Enallopsamia, Flabellum, Lophelia), from global locations covering a large potential range of Nd isotopic compositions. Comparison with ambient seawater measurements yields excellent agreement and suggests that deep-sea corals are reliable archives for seawater Nd isotopes.A parallel study of Nd concentrations in these corals yields distribution coefficients for Nd between seawater and coral aragonite of 1-10, omitting one particular genus (Enallopsamia). The corals and seawater did however not come from exactly the same location, and further investigations are needed to reach robust conclusions on the incorporation of Nd into deep-sea coral aragonite.Lastly, we studied the viability of extracting the Nd isotope signal from fossil deep-sea corals by carrying out stepwise cleaning experiments. Our results show that physical removal of the ferromanganese coating and chemical pre-cleaning have the highest impact on Nd concentrations, but that oxidative/reductive cleaning is also needed to acquire a seawater Nd isotope signal.     

Hydrogen isotopic composition of NBS and IAEA stable isotope water reference samples

The hydrogen isotopic compositions of several isotope water reference samples have been determined on a cycloidal double-collecting isotope ratio mass spectrometer that can resolve HD⁺ from the ‘contaminant’ H₃⁺ ion beam.     

Influence of production variables and starting material on charcoal stable isotopic and molecular characteristics

We present a systematic study on the effect of starting species, gas composition, temperature, particle size and duration of heating upon the molecular and stable isotope composition of high density (mangrove) and low density (pine) wood. In both pine and mangrove, charcoal was depleted in δ¹³C relative to the starting wood by up to 1.6‰ and 0.8‰, respectively. This is attributed predominantly to the progressive loss of isotopically heavier polysaccharides, and kinetic effects of aromatization during heating. However, the pattern of δ¹³C change was dependant upon both starting species and atmosphere, with different structural changes associated with charcoal production from each wood type elucidated by Solid-State ¹³C Nuclear Magnetic Resonance Spectroscopy. These are particularly evident at lower temperatures, where variation in the oxygen content of the production atmosphere results in differences in the thermal degradation of cellulose and lignin. It is concluded that production of charcoal from separate species in identical conditions, or from a single sample exposed to different production variables, can result in significantly different δ¹³C of the resulting material, relative to the initial wood. These results have implications for the use of charcoal isotope composition to infer past environmental change.     

The isotopic composition of plant sulfur

The isotopic composition of sulfur has been studied in plants representative of various regions of the U.S.S.R., two oceanic islands, and atmospheric precipitations on land and in marine areas. In soils, the isotopic composition of sulfur in the atmospheric water varies as a result of sulfate reduction (increase of δ³⁴S of the soil sulfate) and sulfate regeneration from hydrogen sulfide. The sulfur in plants from the oceanic islands has characteristically higher values of δ³⁴S than the sulfur in the plants and in the atmospheric water of the continents. Compared to sea water, the sulfur from the island plants that were studied contains a considerably lesser proportion of the ³⁴S isotope. This can be explained by the significant role in such plants of the sulfur of the atmospheric air masses coming from the continents.     

Chemical composition and stable carbon isotopic ratios of crude oils from Southern Germany

Thirty crude oils were sampled in the South German Molasse Basin. The crude oils were chemically separated into five component groups and their stable carbon isotopic ratios were determined by mass spectrometry. A distinct differentiation of four regionally connected groups can be inferred from the results of the δ¹³C values and chemical analyses. This grouping is in accordance with the present geologic information on the origin of crude oils in the Molasse Basin.The chemistry of crude oils seems to have been influenced by secondary processes in the eastern part of the Molasse Basin.     

用于MC-ICP-MS测定环境样品中铜、锌同位素的化学分离方法

对不同离子交换柱、淋洗体积、盐度、分离次数等一系列影响铜、锌纯化分离效果的条件进行了探讨,确定了环境样品(湖泊沉积物、植物和颗粒物)中铜、锌同位素测定时化学分离的最佳条件。采用AGMP-1(100～200目)阴离子交换树脂,以7mol/LHCl+0.001%H2O2、2mol/LHCl+0.001%H2O2、0.5mol/LHNO3作为淋洗液,分别在适当的体积接收淋洗液,可以有效地分离沉积物、植物和悬浮物等样品中的铜和锌。化学分离过程中Cu和Zn的回收率接近100%,同位素分馏在测试误差范围以内。将此方法应用于对红枫湖和阿哈湖水体悬浮物、植物和鱼类等样品中Cu、Zn的分离,经MC-ICP-MS测试后,准确获得了这些样品的Cu、Zn同位素组成。     

XANES mapping of organic sulfate in three scleractinian coral skeletons

The presence and localization of organic sulfate within coral skeletons are studied by using X-ray absorption near edge structure spectroscopy (XANES) fluorescence. XANES spectra are recorded from four reference sulfur-bearing organic molecules: three amino acids (H-S-C bonds in cysteine; C-S-C bonds in methionine; one disulfide bond C-S-S-C bonds in cystine) and a sulfated sugar (C-SO₄ bonds in chondroitin sulfate). Spectral responses of three coral skeletons show that the sulfated form is extremely dominant in coral aragonite, and practically exclusive within both centres of calcification and the surrounding fibrous tissues of coral septa. Mapping of S-sulfate concentrations in centres and fibres gives us direct evidence of high concentration of organic sulfate in centres of calcification. Additionally, a banding pattern of S-sulfate is visible in fibrous part of the coral septa, evidencing a biochemical zonation that corresponds to the step-by-step growth of fibres.     

Metabolic effects on stable carbon isotopic composition of freshwater bivalve shell Corbicula fluminea

The stable isotopic composition of the bivalve shell has been widely used to reconstruct the pa-laeo-climate and palaeo-environment. The climatic and environmental significance of carbon isotopic composition of the bivalve shell is still in dispute, and incorporation of metabolic carbon can obscure carbon isotope records of dis-solved inorganic carbon. This study deals with freshwater bivalve, Corbicula fluminea aragonite shell. The results indicated that the δ13C values of bivalve shells deposited out of equilibrium with the host water and showed an onto-genic decrease, indicating that there are metabolic effects and more metabolic carbon is incorporated into larger shells. The proportion of metabolic carbon of shells varies between 19.8% and 26.8%. However, δ13CS can still be used as qualitative indicators of δ13CDIC and environmental processes that occurred during shell growth.     

Diurnal variations in the isotopic composition of dissolved inorganic carbon in seawater from coral reef environments

The isotopic composition of total dissolved inorganic carbon in seawater was determined as a function of time of day in coral reef environments at Saipan, Abaiang Atoll, Tahiti, Florida and Heron Island on the Great Barrier Reef of Australia. At each locality water collected during the day was enriched in ¹³C with respect to water collected at night. The form and magnitude of the diurnal cycles is dependent upon the ratio of local biomass to local water mass and on the degree of exchange between local water mass and the open ocean reservoir. Comparison of open and closed system models is made using computer generated δ¹³C vs. time curves to illustrate modulation by the tidal cycle of the simple diurnal variation in a closed system. The results are of geochemical significance in that the δ¹³C of CaCO₃ precipitated in certain environments is dependent on the time of crystallization. This must be taken into account in isotope ratio studies of both plant and animal secreted carbonates which are preferentially precipitated during certain periods of the day.     

The Hf-Nd isotopic composition of marine sediments

This paper presents new major and trace-element data and Lu-Hf and Sm-Nd isotopic compositions for representative suites of marine sediment samples from 14 drill sites outboard of the world’s major subduction zones. These suites and samples were chosen to represent the global range in lithology, Lu/Hf ratios, and sediment flux in subducting sediments worldwide. The data reported here represent the most comprehensive data set on subducting sediments and define the Hf-Nd isotopic variations that occur in oceanic sediments and constrain the processes that caused them.Using new marine sediment data presented here, in conjunction with published data, we derive a new Terrestrial Array given by the equation, ε_Hf = 1.55 × ε_Nd + 1.21. This array was calculated using >3400 present-day Hf and Nd isotope values. The steeper slope and smaller y-intercept of this array, compared to the original expression (ε_Hf = 1.36 × ε_Nd + 2.89; Vervoort et al., 1999) reflects the use of present day values and the unradiogenic Hf of old continental samples included in the array.In order to examine the Hf-Nd isotopic variations in marine sediments, we have classified our samples into 5 groups based on lithology and major and trace-element geochemical compositions: turbidites, terrigenous clays, and volcaniclastic, hydrothermal and hydrogenetic sediments. Compositions along the Terrestrial Array are largely controlled by terrigenous material derived from the continents and delivered to the ocean basins via turbidites, volcaniclastic sediments, and volcanic inputs from magmatic arcs. Compositions below the Terrestrial Array derive from unradiogenic Hf in zircon-rich turbidites. The anomalous compositions above the Terrestrial Array largely reflect the decoupled behavior of Hf and Nd during continental weathering and delivery to the ocean. Both terrigenous and hydrogenetic clays possess anomalously radiogenic Hf, reflecting terrestrial sedimentary and weathering processes on the one hand and marine inheritance on the other. This probably occurs during complementary processes involving preferential retention of unradiogenic Hf on the continents in the form of zircon and release of radiogenic Hf from the breakdown of easily weathered, high Lu-Hf phases such as apatite.     

The oxygen isotopic composition of uranium minerals: A review

Uranium ore is an essential material in the preparation of nuclear fuel for civilian as well as military uses. Uranium is first extracted from uranium-bearing minerals using a variety of reagents, and is precipitated from solutions as yellow cake prior to isotope enrichment processes. The disintegration of the former Eastern Bloc in the 1990s and frequent unrest in the Middle East have underscored the need for better characterizing source uranium ores for forensic and attribution purposes.The world's major deposits of U occur in several distinctly different geological environments. Fourteen principal types of U deposits and rocks with elevated uranium contents are recognized with more than 40 subtypes. Combining our own analysis and literature data, we have amassed over 250 oxygen isotope data from 13 major U-producing countries, which vary widely from − 32 to + 11‰. However, interpreting the oxygen isotopic composition of uraninite in terms of the composition of the fluid from which it precipitated, or interacted with, requires knowledge of the fractionation factor and temperature of interactions, which are not always available. Since each deposit type occurs within a unique geologic setting and is generally formed from chemically distinct fluids, the chemical compositions of the uranium ores are also distinct: uranium deposits that form in igneous rocks have higher trace element compositions relative to sandstone-hosted deposits. Our data shows that one of the most useful techniques for distinguishing between uranium ore is to use a combination of δ¹⁸O values and rare-earth elements (e.g., La/Yb ratios). These methods may allow investigators to trace uranium ore back to the source.     

南海珊瑚礁硼同位素组成及其环境意义

采用正热电离质谱方法测定了中国南海诸岛７０００ａ以来的珊瑚礁的硼同位素的硼含量。讨论了珊瑚礁中硼同位素 硼含量,Ｐ不管不顾忻代等参数的关系。结果表明,所测定的珊瑚礁硼同位素组成变化范围为２２．７￣２４．８‰,并且与珊瑚 硼含量呈正相关关系。根据硼同位素与海水ＰＨ值的关系计算出过去７０００ａ南海泊ＰＨ值变化８．１０￣８．４１。初步探讨了硼同位素组成与南海海平面变化的关系。     

The vanadium isotopic composition of L ordinary chondrites

Stable isotopic data of meteorites are critical for understanding the evolution of terrestrial planets. In this study, we report high-precision vanadium (V) isotopic compositions of 11 unequilibrated and equilibrated L chondrites. Our samples show an average δ⁵¹V of ??1.25‰?±?0.38‰ (2SD, n?=?11), which is ~?0.5‰ lighter than that of the bulk silicate Earth constrained by mantle peridotites. Isotopic fractionation in type 3 ordinary chondrites vary from ??1.76‰ to ??1.29‰, whereas the δ⁵¹V of equilibrated chondrites vary from ??1.37‰ to ??1.08‰. δ⁵¹V of L chondrites do not correlate with thermal metamorphism, shock stage, or weathering degree. Future studies are required to explore the reason for V isotope variation in the solar system.