Sources of fine-sized organic matter in North Atlantic Heinrich Layers: δC and δN tracers

Organic carbon (OC) and total nitrogen (TN) concentrations and stable isotope ratios (δ¹³C, δ¹⁵N) of fine (<50 μm) size fractions of deep-sea sediments from the central North Atlantic were employed to identify changes in sources of organic matter over the past 50 ka BP. Ambient glacial sediments are characterised by values that reflect mixtures of marine and terrestrial inputs (averages ± 1σ: OC/TN = 7.6 ± 0.8; δ¹³C = −22.8 ± 1.0‰; δ¹⁵N = 5.5 ± 0.6‰). δ¹³C, OC, and TN concentrations shift to higher values during the Holocene, indicating a gradual decrease of fine terrigenous supply to the North Atlantic. The unchanged δ¹⁵N record between last glacial and Holocene stages indicates that the central North Atlantic region remained oligotrophic at least during the past 50 ka BP, but additional studies are required to support this result in terms of nitrogen oceanic budget. During the phases of enhanced ice-rafted detrital supply corresponding to prominent Heinrich events (HL₁, HL₂, HL₄, and HL₅), fine-sized sedimentary organic matter has lower OC and TN concentrations, contrasting sharply with those of ambient glacial sediments. Lower δ¹³C (down to −28‰) and δ¹⁵N (down to 1.6‰) values and high OC:TN ratios (up to 14.7 ± 1.1) are found for HL₁, HL₂, and with lesser extent for HL₄. These values reflect enhanced detrital supply originating from poorly differentiated soil horizons that characterise periglacial climate conditions and from organic matter-bearing rock sources of the underlying geological basement. During HL₅, only the δ¹³C offset records the input of fine size ice-rafted organic matter. Gradually changing soil development conditions during the time interval covering HL₅ to HL₁ (marine isotope stages 5 to 2), as well as varying erosion levels, have been hypothesized on the basis of constant δ¹³C, increasing OC/TN and decreasing δ¹⁵N values.     

Sources and distribution of terrigenous organic matter delivered by the Atchafalaya River to sediments in the northern Gulf of Mexico

Suspended sediments (SS) from the Atchafalaya River (AR) and the Mississippi River and surficial sediment samples from seven shallow cross-shelf transects west of the AR in the northern Gulf of Mexico were examined using elemental (%OC, C/N), isotopic (δ¹³C, Δ¹⁴C), and terrigenous biomarker analyses. The organic matter (OM) delivered by the AR is isotopically enriched (∼−24.5‰) and relatively degraded, suggesting that soil-derived OM with a C4 signature is the predominant OM source for these SS. The shelf sediments display OC values that generally decrease seaward within each transect and westward, parallel to the coastline. A strong terrigenous C/N (29) signal is observed in sediments deposited close to the mouth of the river, but values along the remainder of the shelf fall within a narrow range (8-13), with no apparent offshore trends. Depleted stable carbon isotope (δ¹³C) values typical of C3 plant debris (−27‰) are found near the river mouth and become more enriched (−22 to −21‰) offshore. The spatial distribution of lignin in shelf sediments mirrors that of OC, with high lignin yields found inshore relative to that found offshore (water depth > 10 m).The isotopic and biomarker data indicate that at least two types of terrigenous OM are deposited within the study area. Relatively undegraded, C3 plant debris is deposited close to the mouth of the AR, whereas more degraded, isotopically enriched, soil-derived OM appears to be deposited along the remainder of the shelf. An important input from marine carbon is found at the stations offshore from the 10-m isobath. Quantification of the terrigenous component of sedimentary OM is complicated by the heterogeneous composition of the terrigenous end-member. A three-end-member mixing model is therefore required to more accurately evaluate the sources of OM deposited in the study area. The results of the mixing calculation indicate that terrigenous OM (soil-derived OM and vascular plant debris) accounts for ∼79% of the OM deposited as inshore sediments and 66% of OM deposited as offshore sediments. Importantly, the abundance of terrigenous OM is 40% higher in inshore sediments and nearly 85% higher in offshore sediments than indicated by a two-end-member mixing model. Such a result highlights the need to reevaluate the inputs and cycling of soil-derived OM in the coastal ocean.     

Note on the isotopic geochemistry of fossil-lacustrine tufas in carbonate plateau—A study from Dungul region (SW Egypt)

Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)_molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ¹³C_mean = −2.49 ± 0.99‰; δ¹⁸O_mean = −9.43 ± 1.40‰). The δ¹³C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ¹⁸O values are typical of fresh water carbonates. Covariation between δ¹³C and δ¹⁸O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ¹³C_mean = −2.06 ± 0.84‰; δ¹⁸O_mean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)_molar, δ¹³C and δ¹⁸O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records.     

Carbon, oxygen, and strontium isotope geochemistry of carbonate rocks of the upper Miocene Kudankulam Formation, southern India: Implications for paleoenvironment and diagenesis

The carbon, oxygen, and strontium isotope compositions of carbonate rocks from the upper Miocene Kudankulam Formation, southern India, were measured to understand palaeoenvironment and carbonate diagenesis of this formation. Both carbon and oxygen isotope ratios of various carbonate phases including whole rocks, ooids, molluscan mold-fill and sparry pore-fill calcite cements are depleted in ¹⁸O and ¹³C compared to those of contemporaneous seawater, indicating that the Kudankulam carbonates underwent extensive meteoric diagenesis. Based on δ¹³C and δ¹⁸O values for sparry calcite cements (pore-fill and molluscan mold-fill) formed in the meteoric diagenetic realm (δ¹³C from −7.8‰ to −6.0‰ and −9.0‰ to −7.0‰; δ¹⁸O from −9.2‰ to −6.5‰ and −9.4‰ to −2.6‰, respectively), it is interpreted that the diagenetic system was open and was proximal to the vadose water recharge zone. The negative δ¹⁸O values of various carbonate components (about −9.4‰ to −4.1‰ for whole rocks; about −8.4‰ to −2.6‰ for ooids) suggest that during the late Miocene the paleoclimate of the study area was humid, unlike today, probably due to the intense Indian monsoon system. The carbon isotope compositions (−7.9‰ to −3.6‰ for whole rocks; −4.9‰ to −1.5‰ for ooids) are consistent with the interpretation that the paleo-ecosystem comprised a significant proportion of C₄ type plants, supporting a scenario of expansion of C₄ plants during the late Miocene in the Indian subcontinent as far south as the southern tip of India. The ⁸⁷Sr/⁸⁶Sr ratios of the Kudankulam carbonates (0.70920 to 0.72130) are much greater than those of the contemporaneous or modern seawater (between 0.7089 and 0.7091) and show a general decrease up-sequence. Such high Sr isotope ratios indicate significant radiogenic ⁸⁷Sr influx to the system from the Archean rocks exposed in the drainage area, implying that the deep-seated Archean rocks were already exposed in southern India by the late Miocene.     

The origins and behaviour of carbon in a major semi-arid river,the Murray River,Australia, as constrained by carbon isotopes and hydrochemistry

δ¹³C values of dissolved inorganic C (DIC), dissolved organic C (DOC), and particulate organic C (POC) together with δ¹⁸O and δ²H values of water, δ³⁴S values of dissolved SO₄, and major ion concentrations were measured in the Murray River and its tributaries between November 2005 and April 2007 to constrain the origins and behaviour of riverine C. δ¹³C_DIC values in the Murray River vary between −9.5 and −4.7‰ with a range of <3‰ within any sampling round. δ¹³C_DIC values of the tributaries are −11.0‰ to −5.1‰. DIC concentrations of the Murray River increase from ∼25 mg/L in the middle and upper reaches of the river to 45–55 mg/L in the lower reaches. However, the mass ratio of DIC as a proportion of the total dissolved solids (TDS) decreases from ∼0.6–0.7 in the headwaters to ∼0.2–0.3 in the lower reaches of the river, with similar downstream changes in DIC/Cl ratios. This precludes simple evaporative concentration of DIC and is interpreted as the river evading CO₂; this interpretation is consistent with pCO₂ values that are in the range 550–11,200 ppm volume (ppmv), which are far higher than those in equilibrium with the atmosphere (∼360 ppmv). The δ¹³C_DIC values are similar to those that would be produced by the weathering of marine limestone (δ¹³C ∼ 0‰). However, the lack of marine limestones cropping out in the Murray–Darling Basin and the relatively uniform δ¹³C_DIC values of the Murray River (even in upland reaches where the dominant rock types are metamorphosed silicates and granites) make this unlikely. Rather the high pCO₂ values and δ¹³C_DIC values are best explained by a combination of mineralisation of low δ¹³C organic C and evasion to the atmosphere. The rate of these two processes may attain near steady state and control both DIC concentrations and δ¹³C values.     

Stable carbon and nitrogen isotopic compositions of high molecular weight dissolved organic matter from four U.S. estuaries

High molecular weight dissolved organic matter (HMW-DOM) represents an important component of dissolved organic carbon (DOC) in seawater and fresh-waters. In this paper, we report measurements of stable carbon (δ¹³C) isotopic compositions in total lipid, total hydrolyzable amino acid (THAA), total carbohydrate (TCHO) and acid-insoluble “uncharacterized” organic fractions separated from fourteen HMW-DOM samples collected from four U.S. estuaries. In addition, C/N ratio, δ¹³C and stable nitrogen (δ¹⁵N) isotopic compositions were also measured for the bulk HMW-DOM samples. Our results indicate that TCHO and THAA are the dominant organic compound classes, contributing 33-46% and 13-20% of the organic carbon in HMW-DOM while total lipid accounts for only <2% of the organic carbon in the samples. In all samples, a significant fraction (35-49%) of HMW-DOM was included in the acid-insoluble fraction. Distinct differences in isotopic compositions exist among bulk samples, the compound classes and the acid-insoluble fractions. Values of δ¹³C and δ¹⁵N measured for bulk HMW-DOM varied from −22.1 to −30.1‰ and 2.8 to 8.9‰, respectively and varied among the four estuaries studied as well. Among the compound classes, TCHO was more enriched in ¹³C (δ¹³C = −18.5 to −22.8‰) compared with THAA (δ¹³C = −20.0 to −29.6‰) and total lipid (δ¹³C = −25.7 to −30.7‰). The acid-insoluble organic fractions, in general, had depleted ¹³C values (δ¹³C = −23.0 to −34.4‰). Our results indicate that the observed differences in both δ¹³C and δ¹⁵N were mainly due to the differences in sources of organic matter and nitrogen inputs to these estuaries in addition to the microbial processes responsible for isotopic fractionation among the compound classes. Both terrestrial sources and local sewage inputs contribute significantly to the HMW-DOM pool in the estuaries studied and thus had a strong influence on its isotopic signatures.     

Paleowaters in Silurian-Devonian carbonate aquifers: Geochemical evolution of groundwater in the Great Lakes region since the Late Pleistocene

Changes in the climatic conditions during the Late Quaternary and Holocene greatly impacted the hydrology and geochemical evolution of groundwaters in the Great Lakes region. Increased hydraulic gradients from melting of kilometer-thick Pleistocene ice sheets reorganized regional-scale groundwater flow in Paleozoic aquifers in underlying intracratonic basins. Here, we present new elemental and isotopic analyses of 134 groundwaters from Silurian-Devonian carbonate and overlying glacial drift aquifers, along the margins of the Illinois and Michigan basins, to evaluate the paleohydrology, age distribution, and geochemical evolution of confined aquifer systems. This study significantly extends the spatial coverage of previously published groundwaters in carbonate and drift aquifers across the Midcontinent region, and extends into deeper portions of the Illinois and Michigan basins, focused on the freshwater-saline water mixing zones. In addition, the hydrogeochemical data from Silurian-Devonian aquifers were integrated with deeper basinal fluids, and brines in Upper Devonian black shales and underlying Cambrian-Ordovician aquifers to reveal a regionally extensive recharge system of Pleistocene-age waters in glaciated sedimentary basins. Elemental and isotope geochemistry of confined groundwaters in Silurian-Devonian carbonate and glacial drift aquifers show that they have been extensively altered by incongruent dissolution of carbonate minerals, dissolution of halite and anhydrite, cation exchange, microbial processes, and mixing with basinal brines. Carbon isotope values of dissolved inorganic carbon (DIC) range from −10 to −2‰, ⁸⁷Sr/⁸⁶Sr ratios range from 0.7080 to 0.7090, and δ³⁴S-SO₄ values range from +10 to 30‰. A few waters have elevated δ¹³C_DIC values (>15‰) from microbial methanogenesis in adjacent organic-rich Upper Devonian shales. Radiocarbon ages and δ¹⁸O and δD values of confined groundwaters indicate they originated as subglacial recharge beneath the Laurentide Ice Sheet (14-50 ka BP, −15 to −13‰ δ¹⁸O). These paleowaters are isolated from shallow flow systems in overlying glacial drift aquifers by lake-bed clays and/or shales. The presence of isotopically depleted waters in Paleozoic aquifers at relatively shallow depths illustrates the importance of continental glaciation on regional-scale groundwater flow. Modern groundwater flow in the Great Lakes region is primarily restricted to shallow unconfined glacial drift aquifers. Recharge waters in Silurian-Devonian and unconfined drift aquifers have δ¹⁸O values within the range of Holocene precipitation: −11 to −8‰ and −7 to −4.5‰ for northern Michigan and northern Indiana/Ohio, respectively. Carbon and Sr isotope systematics indicate shallow groundwaters evolved through congruent dissolution of carbonate minerals under open and closed system conditions (δ¹³C_DIC = −14.7 to−11.1‰ and ⁸⁷Sr/⁸⁶Sr = 0.7080-0.7103). The distinct elemental and isotope geochemistry of Pleistocene- versus Holocene-age waters further confirms that surficial flow systems are out of contact with the deeper basinal-scale flow systems. These results provide improved understanding of the effects of past climate change on groundwater flow and geochemical processes, which are important for determining the sustainability of present-day water resources and stability of saline fluids in sedimentary basins.     

Indoor and outdoor urban atmospheric CO2: Stable carbon isotope constraints on mixing and mass balance

From July to November 2009, concentrations of CO₂ in 78 samples of ambient air collected in 18 different interior spaces on a university campus in Dallas, Texas (USA) ranged from 386 to 1980 ppm. Corresponding δ¹³C values varied from −8.9‰ to −19.4‰. The CO₂ from 22 samples of outdoor air (also collected on campus) had a more limited range of concentrations from 385 to 447 ppm (avg. = 408 ppm), while δ¹³C values varied from −10.1‰ to −8.4‰ (avg.=-9.0‰). In contrast to ambient indoor and outdoor air, the concentrations of CO₂ exhaled by 38 different individuals ranged from 38,300 to 76,200 ppm (avg. = 55,100 ppm), while δ¹³C values ranged from −24.8‰ to −17.7‰ (avg. = −21.8‰). The residence times of the total air in the interior spaces of this study appear to have been on the order of 10 min with relatively rapid approaches (∼30 min) to steady-state concentrations of ambient CO₂ gas. Collectively, the δ¹³C values of the indoor CO₂ samples were linearly correlated with the reciprocal of CO₂ concentration, exhibiting an intercept of −21.8‰, with r² = 0.99 and p < 0.001 (n = 78). This high degree of linearity for CO₂ data representing 18 interior spaces (with varying numbers of occupants), and the coincidence of the intercept (−21.8‰) with the average δ¹³C value for human-exhaled CO₂ demonstrates simple mixing between two inputs: (1) outdoor CO₂ introduced to the interior spaces by ventilation systems, and (2) CO₂ exhaled by human occupants of those spaces. If such simple binary mixing is a common feature of interior spaces, it suggests that the intercept of a mixing line defined by two data points (CO₂ input from the local ventilation system and CO₂ in the ambient air of the room) could be a reasonable estimate of the average δ¹³C value of the CO₂ exhaled by the human occupants. Thus, such indoor spaces appear to constitute effective “sample vessels” for collection of CO₂ that can be used to determine the average proportions of C₃ and C₄-derived C in the diets of the occupants. For the various groups occupying the rooms sampled in this study, C₄-derived C appears to have constituted ∼40% of the average diet.     

Abundance of mass 47 CO2 in urban air, car exhaust, and human breath

Atmospheric carbon dioxide is widely studied using records of CO₂ mixing ratio, δ¹³C and δ¹⁸O. However, the number and variability of sources and sinks prevents these alone from uniquely defining the budget. Carbon dioxide having a mass of 47 u (principally ¹³C¹⁸O¹⁶O) provides an additional constraint. In particular, the mass 47 anomaly (Δ₄₇) can distinguish between CO₂ produced by high temperature combustion processes vs. low temperature respiratory processes. Δ₄₇ is defined as the abundance of mass 47 isotopologues in excess of that expected for a random distribution of isotopes, where random distribution means that the abundance of an isotopologue is the product of abundances of the isotopes it is composed of and is calculated based on the measured ¹³C and ¹⁸O values. In this study, we estimate the δ¹³C (vs. VPDB), δ¹⁸O (vs. VSMOW), δ47, and Δ₄₇ values of CO₂ from car exhaust and from human breath, by constructing ‘Keeling plots’ using samples that are mixtures of ambient air and CO₂ from these sources. δ47 is defined as , where is the R⁴⁷ value for a hypothetical CO₂ whose δ¹³C_VPDB = 0, δ¹⁸O_VSMOW = 0, and Δ₄₇ = 0. Ambient air in Pasadena, CA, where this study was conducted, varied in [CO₂] from 383 to 404 μmol mol⁻¹, in δ¹³C and δ¹⁸O from −9.2 to −10.2‰ and from 40.6 to 41.9‰, respectively, in δ47 from 32.5 to 33.9‰, and in Δ₄₇ from 0.73 to 0.96‰. Air sampled at varying distances from a car exhaust pipe was enriched in a combustion source having a composition, as determined by a ‘Keeling plot’ intercept, of −24.4 ± 0.2‰ for δ¹³C (similar to the δ¹³C of local gasoline), δ¹⁸O of 29.9 ± 0.4‰, δ47 of 6.6 ± 0.6‰, and Δ₄₇ of 0.41 ± 0.03‰. Both δ¹⁸O and Δ₄₇ values of the car exhaust end-member are consistent with that expected for thermodynamic equilibrium at∼200 °C between CO₂ and water generated by combustion of gasoline-air mixtures. Samples of CO₂ from human breath were found to have δ¹³C and δ¹⁸O values broadly similar to those of car exhaust-air mixtures, −22.3 ± 0.2 and 34.3 ± 0.3‰, respectively, and δ47 of 13.4 ± 0.4‰. Δ₄₇ in human breath was 0.76  ± 0.03‰, similar to that of ambient Pasadena air and higher than that of the car exhaust signature.     

The implications for paleodietary and paleoclimatic reconstructions of intrapopulation variability in the oxygen and carbon isotopes of teeth from modern feral horses

We analyzed the isotopic patterns found in the tooth enamel of modern feral horses from Shackleford Banks, North Carolina (USA), which has a temperate climate and supports primarily C₄ grasslands. Enamel δ¹³C values averaged −4.1‰ with a standard deviation (1σ) of 1.7‰, which corresponds to an average diet of 66 ± 12% C₄ plants. Our results differ from dietary reconstructions from 1978 to 1981, which found that horses consumed 91% C₄ plants. This suggests that horses have increased their consumption of C₃ forbs, likely as a result of the removal of cattle, sheep, and goats from the island. Shackleford surface waters had δ¹⁸O values that averaged −3.3 ± 0.5‰ and −1.3 ± 1.8‰ on the western and eastern ends of the island, respectively. Tooth enamel samples averaged 27.3 ± 1.5‰ and displayed the same range of δ¹⁸O values as surface waters. The variability of both δ¹⁸O and the δ¹³C values among individuals within this population demonstrates that horses from relatively homogenous temperate environments can display a wide range of isotopic values. Given the observed range of isotopic values for modern horses, we suggest that researchers use the mean values of multiple (≥9) equids when attempting to reconstruct average paleodiets and/or paleoenvironmental conditions.     

Archaeal lipids in Neogene dolomites (Monterey and Sisquoc Formations, California) - Planktic versus benthic archaeal sources

The distribution of archaeal lipids, including archaeol and glycerol dibiphytanyl glycerol tetraethers (GDGTs), in dolomite concretions and surrounding sediment from the Monterey Formation (Miocene) and the Sisquoc Formation (Miocene-Pliocene) were examined to distinguish planktic from benthic contributions. For this purpose, dolomites with positive δ¹³C values (+7‰ to +13‰) were chosen; such highly positive values point to pronounced methanogenesis of benthic archaea in the sedimentary column. At first glance, distributions and relative abundances of GDGTs in both dolomites and background sediment were similar, resembling patterns of marine planktic crenarchaea. A contribution of benthic euryarchaea to the GDGT pool became evident only from variations in the δ¹³C values of different biphytanes obtained after ether cleavage of GDGTs. Whereas bi- and tricyclic biphytanes had an isotopic signal typical of planktic archaea (δ¹³C −23.6‰ to −20.5‰ and −23.4‰ to −21.2‰, respectively) for both dolomite and background sediment, acyclic and monocyclic biphytanes showed lower values for dolomite samples (−25.1‰ to −22.6‰ and −27.6‰ to −24.7‰, respectively), indicating a contribution of lipids from benthic archaea. The isoprenoid diether archaeol (δ¹³C −23.9‰ to −22.9‰), assigned to euryarchaea, was only detected in dolomite samples, also reflecting additional input from sedimentary archaea, probably autotrophic methanogens. The occurrence of lipids derived from methanogenic archaea agrees with the strong ¹³C-enrichment of dolomites and with mineral formation taking place in the zone of archaeal methanogenesis. This implies that the lipid biomarker inventory of sedimentary strata needs to be interpreted carefully, as it is often not straightforward to discriminate between input from the water column and sedimentary microbial activity.     

Diet and habitat of toxodont megaherbivores (Mammalia, Notoungulata) from the late Quaternary of South and Central America

The toxodont megaherbivores Toxodon and Mixotoxodon were endemic to South and Central America during the late Quaternary. Isotopic signatures of 47 toxodont teeth were analyzed to reconstruct diet and ancient habitat. Tooth enamel carbon isotope data from six regions of South and Central America indicate significant differences in toxodont diet and local vegetation during the late Quaternary. Toxodonts ranged ecologically from C₃ forest browsers in the Amazon (mean δ¹³C = −13.4‰), to mixed C₃ grazers and/or browsers living either in C₃ grasslands, or mixed C₃ forested and grassland habitats in Honduras (mean δ¹³C = −9.3‰), Buenos Aires province, Argentina (δ¹³C = −8.7‰), and Bahia, Brazil (mean δ¹³C = −8.6‰), to predominantly C₄ grazers in northern Argentina (δ¹³C = −4.4‰), to specialized C₄ grazers in the Chaco of Bolivia (δ¹³C = −0.1‰). Although these toxodonts had very high-crowned teeth classically interpreted for grazing, the isotopic data indicate that these megaherbivores had the evolutionary capacity to feed on a variety of dominant local vegetation. In the ancient Amazon region, carbon isotope data for the toxodonts indicate a C₃-based tropical rainforest habitat with no evidence for grasslands as would be predicted from the Neotropical forest refugia hypothesis.     

Chemostratigraphy of the Tamengo Formation (Corumbá Group,Brazil): A contribution to the calibration of the Ediacaran carbon-isotope curve

The Corumbá Group, cropping out in the southern Paraguay Belt in Brazil, is one of the most complete Ediacaran sedimentary archives of palaeogeographic, climatic, biogeochemical and biotic evolution in southwestern Gondwana. The unit hosts a rich fossil record, including acritarchs, vendotaenids (Vendotaenia, Eoholynia), soft-bodied metazoans (Corumbella) and skeletal fossils (Cloudina, Titanotheca). The Tamengo Formation, made up mainly of limestones and marls, provides a rich bio- and chemostratigraphic record. Several outcrops, formerly assigned to the Cuiabá Group, are here included in the Tamengo Formation on the basis of lithological and chemostratigraphical criteria. High-resolution carbon isotopic analyses are reported for the Tamengo Formation, showing (from base to top): (1) a positive δ¹³C excursion to +4‰ PDB above post-glacial negative values, (2) a negative excursion to −3.5‰ associated with a marked regression and subsequent transgression, (3) a positive excursion to +5.5‰, and (4) a plateau characterized by δ¹³C around +3‰. A U-Pb SHRIMP zircon age of an ash bed interbedded in the upper part of the δ¹³C positive plateau yielded 543 ± 3 Ma, which is considered as the depositional age ( Babinski et al., 2008a). The positive plateau in the upper Tamengo Formation and the preceding positive excursion are ubiquitous features in several successions worldwide, including the Nama Group (Namibia), the Dengying Formation (South China) and the Nafun and Ara groups (Oman). This plateau is constrained between 542 and 551 Ma, thus consistent with the age of the upper Tamengo Formation. The negative excursion of the lower Tamengo Formation may be correlated to the Shuram–Wonoka negative anomaly, although δ¹³C values do not fall beyond −3.5‰ in the Brazilian sections. Sedimentary breccias occur just beneath this negative excursion in the lower Tamengo Formation. One possible interpretation of the origin of these breccias is a glacioeustatic sea-level fall, but a tectonic interpretation cannot be completely ruled out.     

Geochemical characterization of secondary microbial gas occurrence in the Songliao Basin, NE China

A suite of natural gases from the northern Songliao Basin in NE China were characterized for their molecular and carbon isotopic composition. Gases from shallow reservoirs display clear geochemical evidence of alteration by biodegradation, with very high dryness (C₁/C₂₊ > 100), high C₂/C₃ and i-C₄/n-C₄ ratios, high nitrogen content and variable carbon dioxide content. Isotopic values show wide range variations (δ¹³C_CH4 from −79.5‰ to −45.0‰, δ¹³C_C2H6 from −53.7‰ to −32.2‰, δ¹³C_C3H8 from −36.5‰ to −20.1‰, δ¹³C_nC4H10 from −32.7‰ to −24.5‰, and δ¹³C_CO2 from −21.6‰ to +10.5‰). A variety of genetic types can be recognized on the basis of chemical and isotopic composition together with their geological occurrence. Secondary microbial gas generation was masked by primary microbial gas and the mixing of newly generated methane with thermogenic methane already in place in the reservoir can cause very complicated isotopic signatures. System openness also was considered for shallow biodegraded gas accumulations. Gases from the Daqing Anticline are relatively wet with ¹³C enriched methane and ¹³C depleted CO₂, representing typically thermogenic origin. Gases within the Longhupao-Da’an Terrace have variable dryness, ¹³C enriched methane and variable δ¹³C of CO₂, suggesting dominant thermogenic origin and minor secondary microbial methane augment. The Puqian-Ao’nan Uplift contains relatively dry gas with ¹³C depleted methane and ¹³C enriched CO₂, typical for secondary microbial gas with a minor part of thermogenic methane. Gas accumulations in the Western Slope are very dry with low carbon dioxide concentrations. Some gases contain ¹³C depleted methane, ethane and propane, indicating low maturity/primary microbial origin. Recognition of varying genetic gas types in the Songliao Basin helps explain the observed dominance of gas in the shallow reservoir and could serve as an analogue for other similar shallow gas systems.     

Low temperature volatile production at the Lost City Hydrothermal Field, evidence from a hydrogen stable isotope geothermometer

Although commonly utilized in continental geothermal work, the water-hydrogen and methane-hydrogen isotope geothermometers have been neglected in hydrothermal studies. Here we report δD-CH₄ and δD-H₂ values from high-temperature, black smoker-type hydrothermal vents and low-temperature carbonate-hosted samples from the recently discovered Lost City Hydrothermal Field. Methane deuterium content is uniform across the dataset at − 120 ± 12‰. Hydrogen δD values vary from − 420‰ to − 330‰ at high-temperature vents to − 700‰ to − 600‰ at Lost City. The application of several geothermometer equations to a suite of hydrothermal vent volatile samples reveals that predicted temperatures are similar to measured vent temperatures at high-temperature vents, and 20-60 °C higher than those measured at the Lost City vents. We conclude that the overestimation of temperature at Lost City reflects 1) that methane and hydrogen are produced by serpentinization at > 110 °C, and 2) that isotopic equilibrium at temperatures < 70 °C is mediated by microbial sulfate reduction. The successful application of hydrogen isotope geothermometers to low-temperature Lost City hydrothermal samples encourages its employment with low-temperature diffuse hydrothermal fluids.     

The isotopic composition of particulate organic carbon in mountain rivers of Taiwan

Small rivers draining mountain islands are important in the transfer of terrestrial particulate organic carbon (POC) to the oceans. This input has implications for the geochemical stratigraphic record. We have investigated the stable isotopic composition of POC (δ¹³C_org) in rivers draining the mountains of Taiwan. In 15 rivers, the suspended load has a mean δ¹³C_org that ranges from −28.1±0.8‰ to −22.0±0.2‰ (on average 37 samples per river) over the interval of our study. To investigate this variability we have supplemented suspended load data with measurements of POC in bedrock and river bed materials, and constraints on the composition of the terrestrial biomass. Fossil POC in bedrock has a range in δ¹³C_org from −25.4±1.5‰ to −19.7±2.3‰ between the major geological formations. Using coupled δ¹³C_org and N/C we have found evidence in the suspended load for mixing of fossil POC with non-fossil POC from the biosphere. In two rivers outside the Taiwan Central Range anthropogenic land use appears to influence δ¹³C_org, resulting in more variable and lower values than elsewhere. In all other catchments, we have found that 5‰ variability in δ¹³C_org is not controlled by the variable composition of the biomass, but instead by heterogeneous fossil POC.In order to quantify the fraction of suspended load POC derived from non-fossil sources (F_nf) as well as the isotopic composition of fossil POC (δ¹³C_fossil) carried by rivers, we adapt an end-member mixing model. River suspended sediments and bed sediments indicate that mixing of fossil POC results in a negative trend between N/C and δ¹³C_org that is distinct from the addition of non-fossil POC, collapsing multiple fossil POC end-members onto a single mixing trend. As an independent test of the model, F_nf reproduces the fraction modern (F_mod) in our samples, determined from ¹⁴C measurements, to within 0.09 at the 95% confidence level. Over the sampling period, the mean F_nf of suspended load POC was low (0.29 ± 0.02, n = 459), in agreement with observations from other mountain rivers where physical erosion rates are high and fossil POC enters river channels. The mean δ¹³C_fossil in suspended POC varied between −25.2±0.5‰ and −20.2±0.6‰ from catchment to catchment. This variability is primarily controlled by the distribution of the major geological formations. It also covers entirely the range of δ¹³C_org found in marine sediments which is commonly thought to derive from mixing between marine and terrigenous POC. If land-sourced POC is preserved in marine sediments, then changes in the bulk δ¹³C_org observed offshore Taiwan could instead be explained by changes in the onshore provenance of sediment. The range in δ¹³C_org of fossil organic matter in sedimentary rocks exposed at the surface is large and given the importance of these rocks as a source of clastic sediment to the oceans, care should be taken in accounting for fossil POC in marine deposits supplied by active mountain belts.     

Pore water evolution in oilfield sandstones: constraints from oxygen isotope microanalyses of quartz cement

Oxygen isotope microanalyses of authigenic quartz, in combination with temperatures of quartz precipitation constrained by fluid inclusion microthermometry and burial history modelling, are employed to trace the origin and evolution of pore waters in three distinct reservoirs of the Brae Formation in the Miller and Kingfisher Fields (North Sea). Oxygen isotope ratios of quartz cements were measured in situ in nine sandstone thin sections with a Cameca ims-4f ion microprobe. In conjunction with quartz cement paragenesis in the reservoirs, constrained from textural and cathodoluminescence (CL) microscopy studies, pore water evolution was reconstructed from the time of deposition of the sandstones in the Upper Jurassic until the present.CL photomicrographs of quartz overgrowths in the Brae Formation sandstones show three cement zones (A, B and C) which can be related to different oxygen isotope compositions: (1) the earliest, and thinnest, zone A (homogeneous CL pattern with probable δ¹⁸O values between +23‰ and +26‰—direct measurements were not possible) precipitated in the sandstones at temperatures <60 °C; (2) the second zone B (complex CL pattern and directly measured δ¹⁸O values between +15‰ and +18‰) precipitated in the sandstones most likely between 70 and 90 °C; (3) the third zone C (homogeneous CL pattern and directly measured δ¹⁸O values between +16‰ and +22‰) precipitated in the sandstones most likely at temperatures >90 °C. Calculated oxygen isotope compositions of pore waters show that zone A quartz cements, and enclosing concretionary calcite, precipitated from a meteoric-type fluid (∼−7‰) during shallow burial (<1.5 km). Zone B quartz cements precipitated from fluids which evolved in composition from a meteoric-type fluid (δ¹⁸O −7‰) to a more ¹⁸O-enriched fluid (δ¹⁸O −4‰) as burial continued to ∼3.0 km. Data from zone C quartz cements are consistent with further fluid evolution from δ¹⁸O −4‰ to basinal-type fluids with δ¹⁸O similar to the present-day formation water oxygen isotope composition (+0.6‰ at 4.0 km burial). A similar pore water evolution can be derived for all three reservoirs studied, indicating that hydrogeologic evolution was similar across sandstones of the whole Brae Formation.The quartz cement zones observed in the Brae Formation sandstones, and the pore water history derived for the area studied, is analogous to published petrographic and pore water evolution data from the nearby Brent Group reservoirs and from reservoirs located in the Haltenbanken area on the Atlantic margin offshore Norway. Considering quartz cement is a major porosity-occluding phase in many reservoir sandstones, and because pore waters both dissolve quartz and carry the dissolved silica to cementation sites, the data presented are valuable for improving the understanding and prediction of reservoir quality development in sandstones globally.     

Determination of carbon fractionation factor between aqueous carbonate and CO2(g) in two-direction isotope equilibration

The experiments were conducted in the open CO₂ system to find out the equilibrium fractionation between the carbonate ion and CO₂(g). The existence of isotopic equilibrium was checked using the two-direction approach by passing the CO₂−N₂ gases with different δ¹³C compositions (− 1.5‰ and − 23‰) through the carbonate solution with δ¹³C = − 4.2‰. The Δ_{CO3T²⁻−CO2(g)} equilibrium fractionation is given as 6.03 ± 0.17‰ at 25 °C. Discussion is provided about the significance of carbonate complexing in determination of Δ_{CO3T²⁻−CO2(g)} and Δ_{HCO3T⁻−CO2(g)} fractionations. Finally, an isotope numerical model of flow and kinetics of hydration and dehydroxylation is built to predict the isotopic behaviour of the system with time.     

Sulfur and carbon isotope records from 1700 to 800 Ma carbonates of the Jixian section, northern China: Implications for secular isotope variations in Proterozoic seawater and relationships to global supercontinental events

This study is a comprehensive, stable isotope survey of the marine carbonate-dominated, upper Paleo- to lower Neoproterozoic stratigraphy of Jixian County, China. Carbonate-associated sulfate (CAS) was extracted and measured for δ³⁴S_CAS using the same samples analyzed for δ¹³C_carbonate. This integrated proxy approach is a step towards a more comprehensive picture of secular variation in the composition of Proterozoic seawater. We specifically sampled marine carbonate intervals from the lower section of the Chuanlinggou Formation, Changcheng Group (ca. 1700 Ma) to the top of the Jingeryu Formation, Qingbaikou Group (ca. 800 Ma). δ¹³C_carbonate values are mostly negative in the upper Paleoproterozoic Changcheng Group, with an ascending trend from −3‰ to 0‰. We observed variation of approximately 0 ± 1‰ in the Mesoproterozoic Jixian Group, and positive values of +2 ± 2‰ characterize the lower Neoproterozoic Qingbaikou Group. Stratigraphic variations in δ³⁴S_CAS are more remarkable in their ranges and magnitudes, including conspicuously high values exceeding +30‰ in the three intervals at ca. 1700 Ma, 1300-1100 Ma, and 1000-900 Ma. In the Changcheng Group, δ³⁴S_CAS values are typically higher than +25‰, with only a few values of less than +15‰. In contrast, most of the data spanning from the Mesoproterozoic Tieling Formation of the Jixian Group to the lower Neoproterozoic Jingeryu Formation of the Qingbaikou Group are highly variable between +10‰ and +25‰, with some values exceeding +25‰.In the late Paleoproterozoic (1700-1600 Ma), a >10‰ decrease in δ³⁴S_CAS and ∼3‰ increase in δ¹³C_carbonate are coincident with, and likely related to, the breakup of Columbia, a supercontinent that predated Rodinia. Carbon and sulfur isotope data from the Mesoproterozoic, when global tectonic activity was comparatively weaker, fall mostly in the ranges of +15 ± 10‰ and 0 ± 1‰, respectively, but fluctuations of >20‰ for δ³⁴S_CAS and >3‰ for the δ¹³C_carbonate at ca. 1450-1400 Ma may reflect subduction and large-scale magmatic activity in island arcs marking the end of Columbia breakup. From the late Mesoproterozoic (ca. 1300-1100 Ma) to the early Neoproterozoic (ca. 800 Ma), the δ¹³C and δ³⁴S of seawater increased gradually with increasing variability. Most impressive areδ³⁴S_CAS values that exceed +30‰ in two intervals at ca. 1300-1100 Ma and ca. 1000-900 Ma, which may reflect the assembly and early breakup of Rodinia. Although gaps in the record remain, and studies of even higher resolution are warranted, our results suggest that changes in paleoceanographic conditions linked to global tectonics strongly influenced the biogeochemical cycles of C and S. Furthermore, periods of the Proterozoic previously noted for their isotopic invariability show clear isotopic expressions of this tectonic activity.