Correlated trace element “vital effects” in tropical corals: A new geochemical tool for probing biomineralization

Micron-scale variations in the trace-element (TE) composition of tropical coral skeletons were measured using laser-ablation ICP-MS (LA-ICP-MS) as part of an investigation into the chemical processes underlying paleoenvrionmental proxy reconstructions. Fluctuations in B, Mg, Sr, Ba and U were measured at high spatial resolution in two Porites corals from the Great Barrier Reef (Australia), and the fine-scale fluctuations (< ∼1.0 mm) were compared with seasonal TE cycles in a third coral. Fine-scale TE variations were found to have a large amplitude over distances corresponding to less than 1 month growth. Variations were quasi-periodic and appeared to have characteristic wavelengths on weekly (6-7 d) and monthly (28 d) scales, although periodicity was not continuous and variations could not be matched either within or between individual corallites. Fine-scale variations between Mg, Sr and U were significantly correlated with each other (Sr and U are positively correlated, but negatively correlated with Mg). This 3D correlation “vector” has the same slope as the seasonal-scale Mg, Sr and U correlations, suggesting that the same chemical/biologic biomineralization process mediates trace element variations at both timescales. Importantly, the fine-scale variations are too large to be caused directly by daily to monthly fluctuations in sea-surface temperature. This means that seasonal variations in these elements cannot reflect purely inorganic temperature-dependent coprecipitation. Models of physicochemical calcification were developed to test whether changes in calcification rate could explain the trace-element correlations. The calculations show that increases in calcification rate will result in correlated decreases in all TE/Ca ratios. The models reproduce the Sr partition coefficient, trace-element correlation slopes, and amplitude of fine-scale variations for an average calcifying pH of 8.5, varying by ±0.2 pH units. The models, however, predict U partition coefficients which are too low, and cannot reproduce the negative correlation between Mg and the other trace elements, which may be caused by crystallographic factors.     

Carbonate clumped isotope thermometry of deep-sea corals and implications for vital effects

Here we calibrate the carbonate clumped isotope thermometer in modern deep-sea corals. We examined 11 specimens of three species of deep-sea corals and one species of a surface coral spanning a total range in growth temperature of 2-25 °C. External standard errors for individual measurements ranged from 0.005‰ to 0.011‰ (average: 0.0074‰) which corresponds to ∼1-2 °C. External standard errors for replicate measurements of Δ₄₇ in corals ranged from 0.002‰ to 0.014‰ (average: 0.0072‰) which corresponds to 0.4-2.8 °C. We find that skeletal carbonate from deep-sea corals shows the same relationship of Δ₄₇ (the measure of ¹³C-¹⁸O ordering) to temperature as does inorganic calcite. In contrast, the δ¹³ C and δ¹⁸O values of these carbonates (measured simultaneously with Δ₄₇ for every sample) differ markedly from equilibrium with seawater; i.e., these samples exhibit pronounced ‘vital effects’ in their bulk isotopic compositions. We explore several reasons why the clumped isotope compositions of deep-sea coral skeletons exhibit no evidence of a vital effect despite having large conventional isotopic vital effects.     

Boron isotopes as pH proxy: A new look at boron speciation in deep-sea corals using B MAS NMR and EELS

Dissolved boron in modern seawater occurs in the form of two species, trigonal boric acid B(OH)₃ and tetrahedral borate ion . One of the key assumption in the use of boron isotopic compositions of carbonates as pH proxy is that only borate ions, , are incorporated into the carbonate. Here, we investigate the speciation of boron in deep-sea coral microstructures (Lophelia pertusa specimen) by using high field magic angle spinning nuclear magnetic resonance (¹¹B MAS NMR) and electron energy-loss spectroscopy (EELS). We observe both boron coordination species, but in different proportions depending on the coral microstructure, i.e. centres of calcification versus fibres. These results suggest that careful sampling is necessary before performing boron isotopic measurements in deep-sea corals. By combining the proportions of B(OH)₃ and determined by NMR and our previous ion microprobe boron isotope measurements, we propose a new equation for the relation between seawater pH and boron isotopic composition in deep-sea corals.     

Norwegian corals: radiocarbon and stable isotopes in Lophelia pertusa

The ahermatypic coral Lophelia pertusa which produces aragonitic skeletons is widely distributed along the Norwegian coast. Specimens from a number of localities have been analyzed for oxygen and stable carbon isotope composition and ¹⁴C age. Stable isotope ratios of recent corals provide information on growth rate and seasonality of oceanographic conditions. Lophelia can be useful in paleoenvironmental reconstructions. ¹⁴C dates of fossil Lophelia from Drøak in the Oslofjord, collected from 20 m ahove and 40 m below present day sea-level, indicate regional extinction between 8700 and 7800 years ago. We suggest that the extinction resulted from the cut-off of deep waters by a rising sill in connection with the postglacial shoreline displacement. Radiocarbon dating of coral bushes suggests a fairly rapid growth rate as older and younger parts of recent corals do not reveal any difference in activity despite the short time scale of the history of bomb-produced ¹⁴C in the oceans.     

Assessing scleractinian corals as recorders for paleo-pH: Empirical calibration and vital effects

Laboratory experiments on the branching, symbiont-bearing coral genus Porites and Acropora have been carried out to determine the dependence of the skeletal boron isotopic composition (δ¹¹B) on the pH of seawater. The results show a clear relationship similar to previously established empirical calibrations for planktonic foraminifera and inorganic calcite. A −0.6‰ offset exists between P. cylindrica and A. nobilis which is systematic over the pH range of 7.7-8.2. To test whether the δ¹¹B of coral skeletons changes with physiological processes such as photosynthesis and respiration, corals were grown along a depth transect in their natural environment and under controlled conditions in the laboratory at varying light intensities and food supply. Although we also observe an isotopic offset between P. compressa and Montipora verrucosa, neither experimental treatment systematically changed the δ¹¹B of the two species. These findings are encouraging for using the boron isotope paleo-pH proxy in corals, because it appears that seawater pH is the dominant control on the boron isotopic composition in corals.     

Stable isotopes in the ostracod shell: a preliminary study

Oxygen and carbon isotope ratios of Recent ostracods from six localities are presented. The δO¹⁸ data are consistent with precipitation of the shells in isotopic equilibrium with seawater. although additional data are necessary to confirm equilibrium precipitation. No strong correlation between carbon isotope ratios and temperature or salinity were observed for ostracods.     

无定河流域碳氮稳定同位素研究

对黄河中游一条很有特点的高悬沙支流--无定河流域进行了碳氮稳定同位素调查,发现该流域植被的碳氮同位素组成分布范围很广,碳同位素组成呈现出明显的双峰特征,说明该流域生态系统属于C3和C4混合植被类型.植物的氮同位素组成与碳同位素组成之间并不存在相关关系.沿河沉积物中的碳氮同位素组成之间存在有弱负相关性.河水悬浮体中碳氮同位素组成显示出良好的负相关关系,反映出该河悬浮体中主要有2种物质来源以及具保守性的物理混合特征.根据无定河流域植被、土壤、沉积物的碳同位素调查结果,估算出该河流颗粒有机质中C3植物碳的贡献可占75%～80%.河水悬浮体中有机质的控制性来源是中下游陆地侵蚀物质,同样也反映了流域植被的同位素特征,C3植物碳的贡献占优势.初步的研究结果已经证明,在研究河流中生源要素的输送通量与降水及径流过程之间的关系和河流物质与陆地生态环境变化之间的关系时碳氮稳定同位素示踪应该是十分有效的手段.     

Stable isotopes and cellulase activity as evidence for detritus as a food source for juvenile Gulf menhaden

Menhaden are one of the most abundant components of fish communities in Gulf and Atlantic estuaries. Juvenile menhaden have been reported to have zooplankton, phytoplankton, andSpartina-derived detritus in their guts. However, there has been disagreement over the importance of the detritus as a food source. We show, using physiological and stable isotope evidence, that detritus can be used by juvenile Gulf menhaden. Their diet is very roughly 30% detritus- and 70% plankton-based.     

Stable lead isotopes as tracers of groundwater pollution in the water supply for a small village

High lead (Pb) concentration has been measured in the incoming water to the water supply for a small Swedish village since the 1990s. There are several sources of the contamination and the objective of this study was to identify these by analysis of Pb isotopes. Lead has four stable isotopes in nature (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) and the relative proportions of these vary according to their geological source. The study showed that two anthropogenic sources of Pb, a glassworks deposit and a highway, had similar Pb isotope ratios and thus it was not possible to separate them. However, the very high Pb concentration in the glassworks deposit suggested that this is the main source of the very high concentrations observed occasionally in low flow conditions. The soil in the recharge area of the most important well for the water supply had elevated Pb concentrations compared with background values in soils. Moreover, the Pb ratios in this soil differed from those in the anthropogenic sources. Several sites of mineralisation or natural enrichment have been identified in outcrops about 14?km northwest of the site and several anomalies in Pb exist in the glacial till. The conclusion was that Pb originating from the soil in the recharge area generally dominates and leads to Pb concentrations in water of 1?C2???g?L^?1. However, at higher concentrations, e.g. around 10???g?L^?1, water transported in cracks and fissure from the glassworks deposit becomes more important.     

Oxygen self-diffusion “fast-paths” in titanite single crystals and a general method for deconvolving self-diffusion profiles with “tails”

Like most other minerals, titanite rarely if ever forms perfect crystals. In addition to the point defects that might affect lattice diffusion, there may be extended line- or planar defects along which fast diffusion could occur. During the course of an experimental study of oxygen lattice diffusion in titanite, we found that almost all of the ¹⁸O uptake profiles produced in natural titanite crystals departed from the complementary error function solution expected for simple lattice diffusion with a constant surface concentration. Instead, they exhibited “tails” extending deeper into the samples than expected for simple lattice diffusion. The purpose of this contribution is to report on these features—described as “fast-paths” for oxygen diffusion—and outline a method for coping with them in extracting information from diffusion profiles.For both dry and hydrothermal experiments in which the “fast paths” are observed, ¹⁸O was used as the diffusant. In dry experiments, the source material was ¹⁸O-enriched SiO₂ powder, while ¹⁸O-enriched water was used for the hydrothermal experiments. Diffusive uptake profiles of ¹⁸O were measured in all cases by nuclear reaction analysis (NRA) using the ¹⁸O (p,α)¹⁵N reaction [see Zhang X. Y., Cherniak D. J., and Watson E. B. (2006) Oxygen diffusion in titanite: lattice and fast-path diffusion in single crystals. Chem. Geol.235 105-123].In our experiments, different sizes of “tails” (with varying ¹⁸O concentrations) were observed. Theoretically, under the same temperature and pressure conditions, the sizes of tails should be affected by two factors: the diffusion duration and the defect density. For the same experiment duration, the higher the defect density, the larger the “tail”; for the same defect densities, the longer the diffusion duration, the larger the “tail.”The diffusion “tails” could be a result of either planar defects or one-dimensional “pipe” diffusion. AFM imaging of HF etched titanite surfaces confirmed that the etched features might be caused by either parallel planar defects or parallel pipe defects, but could not differentiate between these possibilities. Through theoretical calculations simulating the tailed diffusion profiles using reasonable assumptions of lattice diffusivities and fast-path diffusivities, and comparing these with tail features measured in our samples, it can be concluded that the “tails” observed in our experiments are caused by planar defects rather than pipe defects.A new method was developed for separating the “fast-path” contribution from the overall composite diffusion profile consisting of both “fast-path” and lattice diffusion. Through this process, the lattice diffusion coefficient could be determined, which is required to analyze the tail. The oxygen diffusion rates in the fast-paths were obtained by traditional graphical analysis methods, using the Whipple-Le Claire equation (for 2-D defects) assuming that the width of the fast-path is 1 nm. Two Arrhenius relations were obtained for the fast-path diffusion phenomenon, one for experiments under dry conditions, and the other for hydrothermal conditions:

     

Stable chlorine isotopes in arid non-marine basins: Instances and possible fractionation mechanisms

Stable chlorine isotopes are useful geochemical tracers in processes involving the formation and evolution of evaporitic halite. Halite and dissolved chloride in groundwater that has interacted with halite in arid non-marine basins has a δ³⁷Cl range of 0 ± 3‰, far greater than the range for marine evaporites. Basins characterized by high positive (+1 to +3‰), near-0‰, and negative (−0.3 to −2.6‰) are documented. Halite in weathered crusts of sedimentary rocks has δ³⁷Cl values as high as +5.6‰. Salt-excluding halophyte plants excrete salt with a δ³⁷Cl range of −2.1 to −0.8‰. Differentiated rock chloride sources exist, e.g. in granitoid micas, but cannot provide sufficient chloride to account for the observed data. Single-pass application of known fractionating mechanisms, equilibrium salt-crystal interaction and disequilibrium diffusive transport, cannot account for the large ranges of δ³⁷Cl. Cumulative fractionation as a result of multiple wetting-drying cycles in vadose playas that produce halite crusts can produce observed positive δ³⁷Cl values in hundreds to thousands of cycles. Diffusive isotope fractionation as a result of multiple wetting-drying cycles operating at a spatial scale of 1–10 cm can produce high δ³⁷Cl values in residual halite. Chloride in rainwater is subject to complex fractionation, but develops negative δ³⁷Cl values in certain situations; such may explain halite deposits with bulk negative δ³⁷Cl values. Future field studies will benefit from a better understanding of hydrology and rainwater chemistry, and systematic collection of data for both Cl and Br.     

Stable carbon isotopes in selected granitic,mafic, and ultramafic igneous rocks

Noncarbonate (combustion) and carbonate (acid decomposition) carbon were separately analyzed in 18 granitic rocks from a group of related Tertiary intrusions near Crested Butte, Colorado, and 14 mafic and ultramafic rocks from various localities in the western United States. Among the granites, carbonate carbon ranges from nil to 0.76 per cent with δC¹³-values from ?5.6 to ? 9.0‰ (vs PDB); noncarbonate carbon varies from 32–360 ppm with δC¹³-values from ?19.7 to ?26.6‰, The mafic and ultramafic rocks have carbonate carbon contents ranging from 53 ppm to about 2 per cent with δC¹³-values from + 2.9 to ?10.3‰; noncarbonate carbon varies from 26 to 150 ppm with δC¹³-values of ?22.2 to ? 27.l‰ For these samples, carbonate carbon ranges from 12.0 to 29.4‰ heavier than coexisting noncarbonate carbon. This consistent difference between δC¹³ of carbonate and noncarbonate carbon may be an isotopic fractionation effect. Because the specific indigenous form of noncarbonate (combustion) carbon is in doubt, conclusive interpretations regarding isotopic equilibration and fractionation cannot be made.These results have bearing on the assessment of the isotopic composition of mantle carbon and consequently are germane to the question of the origin (source) and history of crustal carbon. If mantle carbon is isotopically similar to noncarbonate (combustion) carbon, i.e. δC¹³-values from ?19.7 to ? 27.1‰, then a simple mantle degassing source for crustal carbon is improbable. Such a result would indicate an additional source of crustal carbon such as from a primitive atmosphere or extra-terrestrial accretion.     

Effect of hydrogen limitation and temperature on the fractionation of sulfur isotopes by a deep-sea hydrothermal vent sulfate-reducing bacterium

The fractionation of sulfur isotopes by the thermophilic chemolithoautotrophic Thermodesulfatator indicus was explored during sulfate reduction under excess and reduced hydrogen supply, and the full temperature range of growth (40-80 °C). Fractionation of sulfur isotopes measured under reduced H₂ conditions in a fed-batch culture revealed high fractionations (24-37‰) compared to fractionations produced under excess H₂ supply (1-6‰). Higher fractionations correlated with lower sulfate reduction rates. Such high fractionations have never been reported for growth on H₂. For temperature-dependant fractionation experiments cell-specific rates of sulfate reduction increased with increasing temperatures to 70 °C after which sulfate-reduction rates rapidly decreased. Fractionations were relatively high at 40 °C and decreased with increasing temperature from 40-60 °C. Above 60 °C, fractionation trends switched and increased again with increasing temperatures. These temperature-dependant fractionation trends have not previously been reported for growth on H₂ and are not predicted by a generally accepted fractionation model for sulfate reduction, where fractionations are controlled as a function of temperature, by the balance of the exchange of sulfate across the cell membrane, and enzymatic reduction rates of sulfate. Our results are reproduced with a model where fractionation is controlled by differences in the temperature response of enzyme reaction rates and the exchange of sulfate in and out of the cell.     

Stable isotopes in a stalagmite from NW Sweden document environmental changes over the past 4000 years

Sundqvist, H. S., Holmgren, K., Moberg, A., Spötl, C. & Mangini, A. 2009: Stable isotopes in a stalagmite from NW Sweden document environmental changes over the past 4000 years. Boreas, 10.1111/j.1502‐3885.2009.00099.x. ISSN 0300‐9483. This study of a 4000‐year‐old stalagmite from Korallgrottan in northwestern Sweden highlights the potentials and challenges when using stable isotopes in stalagmites as climate proxies, as well as the fact that the relationship between climate and proxy may change through time. Both the oxygen and the carbon isotopes display an overall trend of enrichment together with decreasing growth rates over the time period covered by the stalagmite, which is considered a generally cooling period according to current palaeoclimate understanding. The stable isotope records show enriched isotopic values during the, for Scandinavia, comparatively cold period AD 1300–1700 and depleted values during the warmer period AD 800–1000. The indication of a negative relationship between measured δ¹⁸O and surface temperature concurs with earlier reported stalagmite records from regions with a seasonal snow cover and is further supported by the fact that the stalagmite δ¹⁸O record shows general similarities with both regional and hemispheric temperature reconstructions available for the past 500 and 2000 years, respectively. Compared with a stable isotope record of lacustrine carbonates from northern Sweden, however, shifting correlations over time between the two records indicate that a local hydrological change may have taken place at Korallgrottan, or at the lake, compared with around 1000 years ago. The earlier part of the stalagmite δ¹⁸O might thus be influenced, to some extent, by another process than the later part, which means that a negative relationship between δ¹⁸O and surface temperature might not hold for the entire 4000‐year‐old record.     

四川盆地龙马溪组页岩微裂缝发育的“甜点”效应与机制

系统认识和明确页岩“甜点”层段中有机质和脆性矿物促进微裂缝发育的效应和机制,对于提高水力压裂效率,促进页岩气增产稳产具有重要的工程实践意义。本文系统调研了国内外页岩中有机质和脆性矿物控制下的裂缝发育机理等的研究成果,结合数值模拟,对四川盆地龙马溪组页岩“甜点”层段中微裂缝发育的效应和机制进行了全面剖析和探究。研究结果表明：四川盆地龙马溪组页岩特殊的沉积背景为裂缝的发育提供了良好的物质基础。其中有机质的不同成熟度阶段、空间分布和形状、丰度和有机孔隙都在不同程度上控制着微裂缝的形成和发育。脆性矿物在岩石破坏过程中能量的高效转化和良好的脆性响应机制,促进了裂缝的复杂化。少量裂缝的发育还受控于有机质和脆性矿物接触的力学边界、有机酸的溶蚀以及脆性矿物的嵌入等相关效应与机制,进一步突显了裂缝成因的复杂化。由此,建议未来关于页岩储层的脆性评价工作向多元组分的精细化方向发展,同时注重微米—纳米尺度下有机质和脆性矿物力学性质的表征,对于促进并深化页岩破裂机理的认识具有一定的研究价值。     

Stable carbon isotopes in freshwater mussel shells: Environmental record or marker for metabolic activity?

Mussel shells have been used in a number of paleoecological and environmental studies. The interpretation of stable carbon isotopic composition of shell material is still controversial. The carbon for shell carbonate precipitation can either be derived from ambient dissolved inorganic carbon (DIC), with shells recording environmental signals, or from metabolic CO₂, with the potential to disguise environmental signals. To gain insight into this question, we investigated four nearly 100-yr long-term records of aragonite shells from an extant freshwater bivalve species, the endangered freshwater pearl mussel (Margaritifera margaritifera L.). Single growth increments of the outer prismatic and the inner nacreous zones were successfully and easily separated with a simple heat treatment for chronological analyses of δ¹³C in single layers of each zone. Autocorrelation and semivariance statistical methods reveal that mussels show distinct individual signal patterns, which extend up to 25 yr. Signal patterns are reliably reproduced with replicate samples from defined layers within one shell and show similar patterns with a slight offset for inner nacreous and outer prismatic layers for individual animals. Mussels exposed to the same environmental conditions exhibit distinct and contradictory signature patterns, which do not match between individuals. This observation can only be explained by strong metabolic influences on shell precipitation. Environmental changes in pH, temperature, electric conductivity and atmospheric carbon signature had no or little (<5%) influence, whereas body tissue protein and body tissue δ¹³C signatures negatively correlated with the youngest produced shell δ¹³C signatures, indicating that respiration causes a preferential loss of light isotopes from body mass and an inverse enrichment in shell aragonite. Hence, the shells of the freshwater pearl mussel yield a long-term record of metabolic activity, whereas the use of δ¹³C in these shells as recorder for environmental signals is questionable. This may also be true for shells from other species, for which metabolic carbon incorporation has been acknowledged.     

Stable hydrogen isotopes in iron oxides—isotope effects associated with the dehydration of a natural goethite

The dehydration of a natural goethite to hematite is accompanied by a systematic hydrogen isotope fractionation. Closed system dehydration at, and below, 250°C results in a significantly greater degree of isotopic fractionation than does open system dehydration. This relationship is apparently reversed at 300°C. Both processes produce a progressive decrease in the $\text{D}\text{H}$ ratio of the mineral hydrogen with increasing degree of dehydration. At temperatures of 160°C to 250°C the closed system mineralvapor fractionation factor is independent of temperature, while above 250°C, it varies strongly with temperature. The mineral-vapor fractionation factor associated with open system dehydration appears to be independent of temperature over the interval 160°C to 300°C. The closed system $\text{D}\text{H}$ fractionation suggests that natural goethite undergoing dehydration in the presence of water can isotopically exchange with that water.CO₂ loss from goethite during dehydration is correlated with the loss of H₂O. The CO₃ is thought to be present in carbonates which exist as impurities in the goethite. Loss of both H₂O and CO₂ appears to be diffusion-controlled.