The relationship between total dissolved carbon dioxide and its stable carbon isotope ratio in aquatic sediments

A model is constructed to predict the stable carbon isotope ratio of the total dissolved CO₂ in aquatic sediments and laboratory reactors. The major parameters of the model are the fractionation between CO₂ and CH₄ as well as the intra-molecular fractionation of acetate, the relative production of CH₄ from CO₂ reduction versus acetate fermentation, the net production ratio of CO₂ to CH₄ and the stable carbon isotope ratio of the source organic carbon. The model is fitted to published data and to date from the littoral sediments of Lake Memphremagog, Quebec, Canada. The inclusion of the intra-molecular fractionation factor of acetate in the model provides a good fit to the data; without this factor, the values of the other parameters necessary for a good fit appear unreasonable.     

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 decline and recovery of a persistent Texas brown tide algal bloom in the Laguna Madre (Texas, USA)

The Laguna Madre has experienced a persistent bloom ofAureoumbra lagunensis for over eight years. The persistence of this bloom may be due in part to the often hypersaline conditions in Laguna Madre (40–60 psu) that favor the growth ofA. lagunensis. Above-normal rainfall in the fall of 1997 reduced the salinities in Baffin Bay from >40 to<20 psu.A. lagunensis cell densities dropped from>10⁶ cells ml⁻¹ in July 1997 to c. 200 cells ml⁻¹ in January 1998. During this time of low brown tide density, phytoplankton biomass generally remained high and the Laguna Madre experienced successive blooms of diatoms (Rhizosolenia spp.) and cyanobacteria. Hypersaline conditions returned in 1998 and brown tide densities increased to>0.5 × 10⁶ cells ml⁻¹ by summer. The extraordinary persistence of the brown tide and the unusual sequence of intense blooms may be related in part to the reduction of zooplankton populations. Microzooplankton populations declined following the above-normal rain in the fall of 1997; populations did not recover until fall 1998. Copepod populations also declined sharply and remained low in Laguna Madre, but recovered by summer 1998 in Baffin Bay. Dilution experiments indicated that microzooplankton grazing and phytoplankton growth were usually balanced when measured during our cruises. The rapid recovery of theA. lagunensis bloom suggests that this alga may be a more resilient component of the Laguna Madre flora than previously suspected.     

A mathematical model of the brown tide

A differential equation model is proposed for “brown tide” algae blooms in the coastal waters of Long Island which provides a plausible mechanisms for the underlying dynamics. Growth rates depend on annual variations in temperature and salinity. The maximum population density is effectively limited by the availability of a favorable concentration of nutrients, together with zooplankton grazing. Salinity depends on rainfall while nutrient concentration is influenced by tidal flushing. The first of these factors is aperiodic, the second periodic, in time. The resulting nonlinear model distinguishes between ‘fast’ algae growth and ‘slow’ long-term changes in nutrients and salinity. Because of this one can show that explosive increases of algae densities will occur infrenquently at sporadic intervals. Computer trials with the model appear to replicate many, if not all, the essential features of the observed bloom.     

辽河原油好氧生物降解模拟过程中化学组成及其碳同位素值的变化

对辽河盆地中央凸起南部潜山原油进行了好氧生物降解模拟实验,分析了辽河原油在轻度至中度(PM 1~4级)的好氧生物降解过程中化学组分的变化,以及在此过程中原油族组分和正构烷烃单体的稳定碳同位素值的变化。结果显示,饱和烃组分的消耗速率最快,正构烷烃的消耗速率高于异构烷烃,低碳数正构烷烃的消耗速率高于高碳数正构烷烃。正构烷烃的疏水性及其在原油中的相对浓度可能是影响微生物选择性地消耗正构烷烃的主导因素,即低碳数的正构烷烃由于在油水界面上的表面张力较小而更容易被微生物降解。正构烷烃单体(C_(14)~C_(30))稳定碳同位素值在生物降解过程中较稳定,未产生明显的碳同位素分馏效应。正构烷烃的好氧降解产物主要是脂肪酸、醇和CO_2。辽河原油中正构烷烃组分的δ~(13)C值较饱和烃、芳烃、胶质和沥青质组分都要偏重,降解产物中水溶性较低的高碳数脂肪酸和醇大部分进入胶质中,少部分通过氢键缔合和形成酯键等方式进入到沥青质组分中,造成沥青质组分的δ~(13)C值发生相应的变化,即对沥青质的δ~(13)C值产生"拉动效应";而降解产物中高水溶性的低碳数烷基酸和醇会进入水相而脱离原油,导致残余油的整体δ~(13)C值相应变轻。因此,假如易受生物降解的烃类如正构烷烃等的δ~(13)C值与原油的δ~(13)C值差别比较大,那么生物降解过程中随着原油化学组成的改变,原油本身及其族组分的δ~(13)C值均可能发生明显的变化。     

A contribution to the stable carbon isotope geochemistry of iron meteorites

For most iron meteorites studied, the carbon isotopic composition of nodular graphite falls in the range ?4.8 to ?8.2%. vs PDB and shows a mode between ?5 and ?6%.. Fourteen cohenite analyses from the Magura meteorite fall between ?18.1 and ?19.2%. with a pronounced clustering around ?18.5%.. Carbon of a taenite separate from the same meteorite has an isotopic composition of ?18.8%.; compositions between ?19.7 and ?22.1%. were found for taenite carbon in five other octahedrites. It is suggested that the ¹²C enrichment in cohenite and taenite relative to the nodular graphite is a general phenomenon in iron meteorites, and that the study of ¹³C abundances in iron meteorites may aid in the elucidation of their history. To this end an experimental study of carbon isotope fractionations in the system Fe-Ni-C is essential. The ¹³C content of carbon from several silicate inclusions in the Four Corners and ‘El Taco’ (Campo del Cielo) meteorites is generally similar to the nodular graphite, the ¹²C enrichment (?13%.) in one specimen may be interpreted in terms of a mixing model involving an original inclusion carbon and carbon exsolved from the taenite upon cooling.     

The variations of stable carbon isotope ratio of land plant-derived n-alkanes in deep-sea sediments from the Bering Sea and the North Pacific Ocean during the last 250,000 years

Two piston cores, one located far from the continents (The North Pacific Ocean: ES core), and another located comparatively closer to the continents (The Bering Sea: BOW-8a core) were investigated to reconstruct environmental changes on source land areas. The results show significant contribution of terrestrial organic matter to sediments in both cores. The δ¹³C values of n-C₂₇, n-C₂₉, and n-C₃₁ alkanes in sediments from the North Pacific ES core show significant glacial to interglacial variation whereas those from the Bering Sea core do not. Variations of δ¹³C values of land plant n-alkanes are related to the environmental or vegetational changes in the source land areas. Environmental changes, especially, aridity, rainfall, and pCO₂ during glacial/interglacial transitional periods can affect vegetation, and therefore C₃ / C₄ plant ratios, resulting in δ¹³C changes in the preserved land plant biomarkers. Maximum values of δ¹³C as well as maximum average chain length values of long chain n-alkanes in the ES core occur mostly at the interglacial to glacial transition zones reflecting a time lag related to incorporation of living organic matter into soil and transportation into ocean basins via wind and/or ability of C₄ plants to adapt for a longer period before being replaced by C₃ plants when subjected to gradual climatic changes. Irregular variations with no clear glacial to interglacial trends in the BOW-8a core may result from complex mixture of aerosols from westerly winds and riverine organic matter from the Bering Sea catchments. In addition, terrestrial organic matter entering the Bering Sea could originate from multiple pathways including eolian, riverine, and ice rafted debris, and possibly be disturbed by turbidity and other local currents which can induce re-suspension and re-sedimentation causing an obliterated time relation in the Bering Sea biomarker records.     

Quantification of photosynthetic inorganic carbon utilisation via a bidirectional stable carbon isotope tracer

The amount of bicarbonate utilised by plants is usually ignored because of limited measurement methods. Accordingly, this study quantified the photosynthetic assimilation of inorganic carbon (CO₂ and HCO₃ ^?) by plants. The net photosynthetic CO₂ assimilation (P _N), the photosynthetic assimilation of CO₂ and bicarbonate (P _N’), the proportion of increased leaf area (f _LA) and the stable carbon isotope composition (δ¹³C) of Orychophragmus violaceus (Ov) and Brassica juncea (Bj) under three bicarbonate levels (5, 10 and 15 mm NaHCO₃) were examined to determine the relationship among P _N, P _N’ and f _LA. P _N’, not P _N, changed synchronously with f _LA. Moreover, the proportions of exogenous bicarbonate and total bicarbonate (including exogenous bicarbonate and dissolved CO₂-generated bicarbonate) utilised by Ov were 2.27 % and 5.28 % at 5 mm bicarbonate, 7.06 % and 13.28 % at 10 mm bicarbonate, and 8.55 % and 17.31 % at 15 mm bicarbonate, respectively. Meanwhile, the proportions of exogenous bicarbonate and total bicarbonate utilised by Bj were 1.77 % and 3.28 % at 5 mm bicarbonate, 2.11 % and 3.10 % at 10 mm bicarbonate, and 2.36 % and 3.09 % at 15 mm bicarbonate, respectively. Therefore, the dissolved CO₂-generated bicarbonate and exogenous bicarbonate are important sources of inorganic carbon for plants.     

Correction of tree ring stable carbon isotope chronologies for changes in the carbon dioxide content of the atmosphere

Tree-ring stable carbon isotope ratios (δ¹³C) often display a decline over the industrial period (post-AD1850) that is only partly explained by changes in the isotopic ratio of carbon dioxide (CO₂) and may represent a response to increased atmospheric concentrations of CO₂ (ca). If this is not addressed, reconstructions using long tree-ring stable isotope chronologies calibrated using the modern period, for which meteorological records are available, may be compromised. We propose a correction procedure that attempts to calculate the δ¹³C values that would have been obtained under pre-industrial conditions. The correction procedure uses nonlinear (loess) regression but the magnitude of the adjustment made is restricted by two logical constraints based on the physiological response of trees: first, that a unit increase in ca cannot result in more than the same unit increase in the internal concentration of CO₂ (ci), and second, that increases in water-use efficiency as a result of an increase in ca are limited to maintaining a constant ci/ca ratio. The first constraint allows retention of a falling trend in δ¹³C, which exceeds that which could logically be attributed to a passive response to rising ca. The second constraint ensures that any increase in δ¹³C, reflecting a change in water-use efficiency beyond maintenance of a constant ci/ca, is not removed. The procedure is tested using ‘pseudoproxies’, to demonstrate the effect of the correction on time-series with different shapes, and data from three sites in Finland and Norway. Two of the time-series retain a significant trend after correction, and in all three cases the correction improves the correlation with local meteorological measurements.     

重庆地区岩溶地下河水溶解无机碳及其稳定同位素特征

稳定碳同位素是指示岩溶动力系统碳来源及转化的重要指标。为揭示重庆地区岩溶地下水中溶解无机碳基本特征和碳来源,本文对该地区63条岩溶地下河水样进行了水化学和碳同位素分析。研究结果表明,重庆地区地下河水溶解无机碳主要表现形式为HCO3-,雨季由于稀释作用其浓度低于旱季。重庆岩溶地下河水δ13C-DIC（V-PDB）旱季变化范围为-15.34 ‰～-5.89 ‰,雨季变化范围为-17.40 ‰～-4.23 ‰。根据δ13C同位素质量平衡方法,计算得到重庆地下河旱季碳酸盐岩溶蚀对DIC贡献为45.1 % ～79.7 %,雨季平均为34.6 %～82.1 % 。计算结果表明,在人类活动不断增强的情况下,岩溶水体DIC通量中碳酸盐岩溶解来源的DIC和其参与岩溶地下水δ13C值的形成并不一定是岩溶作用理论方程中所计算的50 %,而是有一定的变化范围。因此在计算岩溶作用碳汇时,建议通过δ13C值扣除碳酸盐岩溶蚀形成DIC的通量后再来推算岩溶作用形成的碳汇量。     

Some observations on the stable carbon isotope composition of dissolved and particulate organic carbon in the marine environment

δ¹³C_PDB compositions for 39 samples of dissolved organic carbon (DOC) from the Gulf of Mexico-Caribbean Sea-Atlantic Ocean system, the South Pacific and Ross Sea are reported. Deep water values are similar with a mean of ?21.8%. attesting to the homogeneity of the oceanic DOC pool. In Antarctic waters, a 5%. difference between DOC and particulate organic carbon (POC), with POC having values similar to modern plankton (δ¹³C_PDB approx ?27%.) supports the idea of the transient nature of POC as compared to DOC.Total, lipid, acid hydrolyzed, amino acid and residue fractions of POC are about 5, 3, 7, 5 and 3%. respectively, more negative in 2000 m water as compared to surface water samples from the Gulf of Mexico.     

Stable carbon isotope ratio variations of organic matter in Orca Basin sediments

Orca Basin is a highly reducing basin on the slope of the Gulf of Mexico. Stable carbon isotope ratios and total organic carbon percentages were determined for two cores within the basin and one control core outside the basin. The results show that the organic carbon content of the basin cores is consistently 2–3 times greater than that of the control core. The Pleistocene-Holocene boundary, indicated by a break in the δ¹³C depth profile, occurs at a greater sediment depth in the basin cores than in the control core. A small sampling interval has made it possible to detect an unexplained fine structure in the δ¹³C profile not previously observed.     

A review of various factors influencing the stable carbon isotope ratio of organic lake sediments by the change from glacial to post-glacial environmental conditions

A survey is made of various factors influencing the ${}^{13}\text{C}{}^{12}\text{C}$ ratio of the organic component in lake sediments, focusing on the behaviour at the change from glacial to post-glacial environmental conditions.Increase in the ¹³C content of the organic sediment is caused by increase in temperature and the corresponding decrease of the supply of molecular CO₂ in the water of the lakes. An increase in the rate of organic production in the lakes may also, perhaps, cause a corresponding ¹³C increase. An increase of the fermentation of organic mud in the lakes may also have an effect in the same direction.Decrease in the ¹³C content of the organic sediment is caused by the change of the relative amounts of production of plankton and submersed macrophytes in the lakes from mainly submersed macrophytes to mainly plankton. A decrease towards almost complete absence of bicarbonate and CO₂ originating from carbonate rocks will also lead to a ¹³C decrease in the organic sediments. The same effect has the change of the terrestrial vegetation cover from almost complete absence to complete cover. A possible decrease of the ¹³C content in the atmospheric CO₂ has an effect in the same direction.     

Variations in carbon and oxygen isotope ratios as a possible guide to ore

Contour maps showing variations in carbon and oxygen isotope ratios may be useful as a guide to ore. Previous literature suggests that the isotopic composition of carbon is related to the environment in which it is deposited. Sedimentary syngenetic ore deposits are also related to the depositional environment in which they occur and should therefore be related to the isotopic composition of the carbon deposited along with the ore. Although metamorphism may obscure palaeontological and stratigraphic indicators of environment, the isotopic composition of organic carbon appears to be unaffected by it. Previous literature suggests that variations in oxygen isotopes can be used also as a guide to certain epigenetic ore deposits.

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Zusammenfassung Isotopenverteilungskarten sind nützliche Hilfsmittel bei der Erzprospektion. In der Literature wird auf die Abhängigkeit der Isotopen-Zusammensetzung vom Ablagerungsmilieu aufmerksam gemacht. Sedimentäre syngenetische Erzlagerstätten sind ohne Zweifel vom Ablagerungsmilieu abhängig. Es liegt deshalb nahe, die Isotopen-Zusammensetzung des darin enthaltenen Kohlenstoffs mit derjenigen der erzbildenden chemischen Elemente zu vergleichen. Obwohl metamorphe Prozesse paläontologische und stratigraphische Prozesse verwischen können, scheint die Isotopen-Zusammensetzung davon unbeeinflußt zu bleiben. Als Hilfsmittel können weiterhin die in der Literatur beschriebenen Isotopenverhältnisse des Sauerstoffs herangezogen werden.

     

Contemporary lead concentration and stable lead isotope ratio distribution in forest moss across the Czech Republic

Lead concentrations and stable lead isotopes (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) were measured in forest moss samples (Pleurozium schreberi or Scleropodium purum) collected at 273 sites across the Czech Republic during 2010. Continuously decreasing median Pb concentrations in moss were documented over the last two decades: 1995: 11 mg/kg, 2000: 5.66 mg/kg, 2005: 4.94 mg/kg and 2010: 2.85 mg/kg. Several local anomalies have decreased in scale, the overall regional distribution patterns remained, however, the same. The regional Pb isotope ratio distributions show that the ratios show little variation for a large central part of the country and provide the large-scale background isotope ratios for the Czech Republic of about ²⁰⁴Pb/²⁰⁶Pb = 0.0550, ²⁰⁶Pb/²⁰⁷Pb = 1.167, ²⁰⁶Pb/²⁰⁸Pb = 0.478 and ²⁰⁷Pb/²⁰⁸Pb = 0.409 for 2010. This background Pb isotope ratio signal in moss has been locally (900–7500 km²) modified by specific Pb isotopic ratio signals caused by deposition of Pb emissions from known local anthropogenic Pb emission sources, such as industrial combustion of local coal, and a variety of industrial enterprises (metallurgical, engineering and glass works). At some sites where mining of uranium and polymetallic ores took place the moss samples show also a locally specific Pb isotope signal. The in terms of area affected largest deviations in the Pb-isotope ratios, e.g., in the Bohemian Massif, may be due to the input of geogenic dust.     

Compositional differences in enstatite chondrites based on carbon and nitrogen stable isotope measurements

Carbon and nitrogen abundance and isotopic compositions, from four EH4, one EH5, five EL6 chondrites and one aubrite, were determined by using stepped pyrolysis (N only) and combustion (N and C) extractions in attempts to distinguish the components present. Carbon contents range from 0.15 to 0.70 wt%, with no systematic relationship between carbon content and meteorite group or petrologic type. Whole-rock δ¹³C values range from −28.5 to −4.1 %., Most C occurs as graphite and when temperature steps above 700°C are considered, there is a difference between EH4,5 (δ¹³C = −9.1 to -5.8%.) and EL6 chondrites (δ¹³C = −6.7 to +4.2%.). Carbon in Bustee aubrite is isotopically lighter (δ¹³C = −24%.) than in any enstatite chondrite.

Nitrogen occurs as osbornite, sinoite and in isostructural substitution for oxygen in silicate lattice sites. Nitrogen abundances and isotopic compositions are more variable than C, due to the heterogenous distribution of N-bearing minerals. Three EL6's containing osbornite have higher N concentrations than other type 6 enstatite chondrites. Sinoite, where present, is depleted in ¹⁵N relative to osbornite. Nitrogen in the Bustee aubrite has a similar abundance and δ¹⁵N value to those of EL6's, again dominated by the presence of osbornite.

In addition to the refractory C-and N-bearing minerals there is also organic material (largely terrestrial contamination) and evidence for at least two “exotic” components. The first is a host for Xe (HL) and is characterized by δ¹³C <-−47%. and δ¹⁵N ≤−73%., whereas the second is less well-defined, but is marked by δ¹⁵N = +269%.     

Fluid heterogeneity during granulite facies metamorphism in the Adirondacks: stable isotope evidence

The preservation of premetamorphic, whole-rock oxygen isotope ratios in Adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived, hot CO₂-H₂O fluids during granulite facies metamorphism. This conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations. The data suggest that these rocks were not an open system during metamorphism; that fluid/rock ratios were in many instances between 0.0 and 0.1; that externally derived fluids, as well as fluids derived by metamorphic volatilization, rose along localized channels and were not pervasive; and thus that no single generalization can be applied to metamorphic fluid conditions in the Adirondacks.Analyses of 3 to 4 coexisting minerals from Adirondack marbles show that isotopic equilibrium was attained at the peak of granulite and upper amphibolite facies metamorphism. Thus the isotopic compositions of metamorphic fluids can be inferred from analyses of carbonates and fluid budgets can be constructed.Carbonates from the granulite facies are on average, isotopically similar to those from lower grade or unmetamorphosed limestones of the same age showing that no large isotopic shifts accompanied high grade metamorphism. Equilibrium calculations indicate that small decreases in ¹⁸O, averaging 1 permil, result from volatilization reactions for Adirondack rock compositions. Additional small differences between amphibolite and granulite facies marbles are due to systematic lithologie differences.The range of Adirondack carbonate ¹⁸O values (12.3 to 27.2) can be explained by the highly variable isotopic compositions of unmetamorphosed limestones in conjunction with minor ¹⁸O and ¹³C depletions caused by metamorphic volatilization suggesting that many (and possibly most) marbles have closely preserved their premetamorphic isotopic compositions. Such preservation is particularly evident in instances of high ¹⁸O calcites (25.0 to 27.2), low ¹⁸O wollastonites (–1.3 to 3.5), and sharp gradients in ¹⁸O (18 permil/15m between marble and anorthosite, 8 permil/25 m in metasediments, and 6 permil/1 m in skarn).Isotopic exchange is seen across marble-anorthosite and marble-granite contacts only at the scale of a few meters. Small (<5 m) marble xenoliths are in approximate exchange equilibrium with their hosts, but for larger xenoliths and layers of marble there is no evidence of exchange at distances greater than 10 m from meta-igneous contacts.     

Using stable isotope analyses to assess carbon dynamics in a shallow subtropical estuary

The sources of carbon, which fuel water column respiration, remain unresolved for most estuaries; our objective was to examine carbon dynamics in a shallow subtropical estuary. We sampled the Sabine-Neches estuary, Texas, during low (November 1999) and high (May 2000) freshwater inflow and measured stable carbon isotope ratios of the dissolved inorganic and orgnaic carbon (δ¹³C-DIC, δ¹³C-DOC), as well as quantifying accessory parameters (salinity, nutrients, total suspended solids, and photosynthetic pigments). Pigment analysis indicated that diatoms were the predominant phytoplankton. Data from the May 2000 sampling event exhibited conservative mixing, indicating that the system was acting as a conduit between the watershed and the Gulf of Mexico. During November, mixing was generally nonconservative indicating extensive recycling of allochthonous and autochthonous carbon sources. Our data imply that both carbon sources had similar isotope, ratios that made it impossible to unambiguously determine the dominant source supporting respiration. The nonconservative DIC concentration data indicating an autotrophic sink as well as the strong relationship between δ¹³C-DOC and chlorophylla, suggest that in situ production was an important component of the DOC pool. We hypothesize that uncharacteristically calm wind conditions during sampling may have promoted phytoplankton settling, removing autotrophs, from the water column, but leaving behind a dissolved biogeochemical signature. Interpretation of carbon dynamics may be confounded by spatial and temporal decoupling of producers and consumers from biogeochemical indicators.