Radiocarbon dating of small terrestrial gastropod shells in North America

Fossil shells of small terrestrial gastropods are commonly preserved in wetland, alluvial, loess, and glacial deposits, as well as in sediments at many archeological sites. These shells are composed largely of aragonite (CaCO₃) and potentially could be used for radiocarbon dating, but they must meet two criteria before their ¹⁴C ages can be considered to be reliable: (1) when gastropods are alive, the ¹⁴C activity of their shells must be in equilibrium with the ¹⁴C activity of the atmosphere, and (2) after burial, their shells must behave as closed systems with respect to carbon. To evaluate the first criterion, we conducted a comprehensive examination of the ¹⁴C content of the most common small terrestrial gastropods in North America, including 247 AMS measurements of modern shell material (3749 individual shells) from 46 different species. The modern gastropods that we analyzed were all collected from habitats on carbonate terrain and, therefore, the data presented here represent worst-case scenarios. In sum, ～78% of the shell aliquots that we analyzed did not contain dead carbon from limestone or other carbonate rocks even though it was readily available at all sites, 12% of the aliquots contained between 5 and 10% dead carbon, and a few (3% of the total) contained more than 10%. These results are significantly lower than the 20–30% dead carbon that has been reported previously for larger taxa living in carbonate terrain. For the second criterion, we report a case study from the American Midwest in which we analyzed fossil shells of small terrestrial gastropods (7 taxa; 18 AMS measurements; 173 individual shells) recovered from late-Pleistocene sediments. The fossil shells yielded ¹⁴C ages that were statistically indistinguishable from ¹⁴C ages of well-preserved plant macrofossils from the same stratum. Although just one site, these results suggest that small terrestrial gastropod shells may behave as closed systems with respect to carbon over geologic timescales. More work on this subject is needed, but if our case study site is representative of other sites, then fossil shells of some small terrestrial gastropods, including at least five common genera, Catinella, Columella, Discus, Gastrocopta, and Succinea, should yield reliable ¹⁴C ages, regardless of the local geologic substrate.     

The role of gypsum and/or dolomite dissolution in tufa precipitation: lessons from the hydrochemistry of a carbonate–sulphate karst system

The precipitation of freshwater carbonates (tufa) along karstic rivers is enhanced by degassing of carbon dioxide (CO₂) downstream of karstic springs. However, in most karstic springs CO₂ degassing is not enough to force the precipitation of tufa sediments. Little is known about the role of dissolution of gypsum or dolomite in the hydrochemistry of these systems and how this affects the formation of tufa deposits. Here we present a monitoring study conducted over a year in Trabaque River (Spain). The river has typical karst hydrological dynamics with water sinking upstream and re‐emerging downstream of the canyon. Mixing of calcium–magnesium bicarbonate and calcium sulphate waters downstream of the sink enhances the dissolution of carbonates and potentially plays a positive role in the formation of tufa sediments. However, due to the common‐ion effect, dissolution of dolomite and/or gypsum causes precipitation of underground calcite cements as part of the incongruent dissolution of dolomite/dedolomitization process, which limits the precipitation of tufa sediments. Current precipitation of tufa is scant compared to previous Holocene tufa deposits, which likely precipitated from solutions with higher saturation indexes of calcite (SIcc values) than nowadays. Limited incongruent dissolution of dolomite/dedolomitization favours higher SIcc values. This circumstance occurs when waters with relatively high supersaturation of dolomite and low SO₄^2? composition sink in the upper sector of the canyon. In such a scenario, the process of mixing waters enhances the exclusive dissolution of limestones, preventing the precipitation of calcite within the aquifer and favouring the increase of SIcc values downstream of the springs. Such conditions were recorded during periods of high water level of the aquifers and during floods. This research shows that the common‐ion effect caused by the dissolution of gypsum and/or dolomite rocks can limit [or favour] the precipitation of tufa sediments depending on the occurrence [or not] of incongruent dissolution of dolomite/dedolomitization. Copyright © 2016 John Wiley & Sons, Ltd.     

Radiocarbon age anomalies of land snail shells in the Chinese Loess Plateau

In the Chinese Loess Plateau, land snail shells are often the only material available for dating in paleoenvironmental and archaeological research. However, the geochronological suitability of land snail shells is limited because of poor knowledge about their deposition dynamics, particularly with regards to the incorporation of inorganic carbonate and the resulting age anomalies. To evaluate the factors controlling these age anomalies, radiocarbon and stable carbon analyses were carried out on surface soils, as well as the shells and organic bodies of different modern snail species from different ecological habitats. The results showed that all specimens were depleted in ¹⁴C, indicating the influence of inorganic, radiocarbon-free carbonate on the ¹⁴C-activity of the snail shells. The apparent ¹⁴C-deficiencies and the resultant age anomalies of both the Cathaica and the Bradybaena snail shells were within close ranges across the Chinese Loess Plateau, indicating that the shells of these species could, after corrections for radiocarbon anomalies, provide reliable age estimates. The apparent ¹⁴C-deficiencies were closely associated with the ecological habitats of the snails. The shells of the ground-dwelling Bradybaena had the smallest age offsets (533 ± 150 a), followed grass-dwelling Cathaica (1107 ± 138 a) and Cathaica living on trees (1550 ± 345 a). These results suggest that the availability of calcium in the respective ecological habitats is an important factor in explaining the apparent ¹⁴C-deficiencies. The influence of carbonate on the stable carbon isotope composition of shells is overwhelmed by the organic diets of snails, making δ¹³C unsuitable for identifying and correcting shell age anomalies. The radiocarbon activities of surface soils (A_calc) increase with weathering intensity. Thus, a significant uncertainty could be caused by assuming that A_calc is zero when estimating the proportions of different carbon sources in shells, as has been the case in most previous studies.     

Exploring the dating of “dirty” speleothems and cave sinters using radiocarbon dating of preserved organic matter

Speleothems and other carbonate deposits such as tufa containing high proportions of detrital material can be difficult to chemically date due to detrital thorium levels causing a high level of error in conventional U-Th disequilibrium dating. Here we investigate the use of an alternative technique centring on radiocarbon dating of organic matter preserved within the detrital fraction. Non-acid soluble humic, particulate and detritally absorbed organic matter was recovered from eight samples from a flowstone sinter formed within a roman aqueduct at Trento in Italy with a maximum age of 100 CE (1850 cal yr BP), and two repeat samples from a dripstone formed within the 20th Century on a wire fence at Lilly-Pilly Cave, Buchan Caves Reserve in Victoria, Australia. In the aqueduct samples the median calibrated ¹⁴C ages ranged from 2232 to 2889 cal yr BP, with 95.4% probability age range in the youngest and oldest samples of 2153–2337 and 2342–3449 cal yr BP respectively. The median age of the more modern dripstone was 336 cal yr BP, with a 95.4% probability age range of 148–486 cal yr BP. These results provide very approximate ball-park estimates of the age of the sample, but are consistently too old when compared to the known maximum ages of formation. It is hypothesised that this offset is due to a combination of the nature of the organic carbon transported from the source organic matter pools, and reworking of both modern and old organic carbon by in situ microbial communities.     

Early diagenetic imprints and U–Th isotope systematics of fossil land snail shells from the Chinese Loess Plateau

The loess-paleosol sequence on the Chinese Loess Plateau provides a unique archive that records climate change in East Asia in the Quaternary, yet absolute dating of the loess deposits is challenging due to the lack of directly datable materials. Fossil land snail shells, which are made from aragonite, are widely preserved in the loess deposits and have long been used to reconstruct past environmental changes. U-series dating of fossil land snail shells has the potential to provide a route for absolute dating of the loess deposits but remains largely unexplored. In this study, we present the first systematic investigation on the U-series isotope geochemistry as well as the early diagenetic imprints of fossil land snail shells (Cathaica sp.) from the Mangshan loess-paleosol sequence in Henan province, central China. Several geochemical techniques, including Raman microscopy, SEM, LA-ICPMS, LA-MC-ICPMS, solution-MC-ICPMS, and AMS ¹⁴C dating, were employed to investigate the mineralogy, chemical and isotopic compositions of both modern and fossil snail shells to micrometer level. Our results show that the fossil Cathaica sp. shells are overall characterized by a higher degree of porosity and elevated contents of organic matter compared to live-collected shells of the same species. The layers with higher porosity and organic matter content in the fossil Cathaica sp. shell are also found to be enriched in Na, Mg, Mn, Ba, and U, indicating diffusion and adsorption of these elements by specific surface binding sites of either aragonitic lattice or organic compounds of the fossil shell. Combining in-situ measurements using LA-MC-ICPMS with solution U-series determination, we further demonstrate that fossil Cathaica sp. shell is relatively homogeneous regrading both [²³⁴U/²³⁸U] and [²³⁰Th/²³⁸U] values although the distribution of U in the fossil shell is sample-specific. The comparison of different dating results suggests that the calculated apparent closed system U–Th ages are all systematically younger (∼6000 to 13,000 years) than the corresponding shell ¹⁴C ages and quartz SAR (single-aliquot regenerative-dose) ages from the Mangshan section. We suggest that the underestimation of U–Th ages of fossil Cathaica sp. shells is very likely caused by diagenetic uptake of U that started immediately after the burial of the shell and effectively ceased when the fossil shell was isolated from the pore waters due to persistent deposition of eolian dust at the Mangshan section. Our work on both modern and fossil Cathaica sp. shells thus provides detailed morphological and geochemical characterization for the diagenetic alteration of fossil snail shells and suggests that U-series dating of fossil land snail shells may provide age constraints for dust deposits in the semi-arid region although the timing of early diagenetic U-uptake by the fossil shells need to be better quantified for reliable age determination.     

The radiocarbon reservoir effect in proglacial lakes: Examples from Antarctica

We studied the apparently old radiocarbon ages from lakes in the dry valleys of Antarctica. The radiocarbon reservoir effect in these lakes results from two components: the inherited age and the residence age. The inherited age is derived from input of old carbon, primarily from subsurface melt of adjacent glaciers. The residence age comes from in situ aging of lake water in an environment sealed from the atmosphere. Our results indicate that surface melt of glaciers introduces little ancient carbon to the lake system, because of rapid gas equilibration with the atmosphere. Subsurface melt in lakes with large glacier cross-sectional areas at the grounding line, however, can contribute a significant amount of ancient carbon, leading to lake-bottom reservoir effects in excess of ∼ 2700 yr. This value can increase to ∼ 20,000 yr immediately at the grounding line. In most lakes, however, surface melt far exceeds that from the subsurface and dilutes the effect of ancient carbon, making the inherited age relatively low. Residence ages generally are on the order of a few thousand years, but can be as much as ∼ 10,000 yr. Because a residence age is reset when the lake loses its ice cover and is exposed to wind-driven mixing, its magnitude can provide important information about lake history.     

U–Th dating of carbonate nodules from methane seeps off Joetsu, Eastern Margin of Japan Sea

We performed U–Th radioactive disequilibrium analyses of carbonate nodules and sediment samples recovered from methane seep sites off Joetsu, of the eastern margin of Japan Sea, to decipher the active period of the methane seep. The carbonates contain ²³⁰Th, part of which is located in detritus such as silicate and organics, at the time of precipitation. The initial ²³⁰Th renders accurate dating with U–Th radioactive disequilibrium method difficult. We assessed the feasibility of correction using radioactive disequilibrium data of ambient sediment to overcome this difficulty. A (²³⁰Th/²³²Th)–(²³⁴U/²³²Th) isochron drawn by three chips divided from a carbonate nodule (PC05-04-50) passed through data points of local sediments. We conclude that the problem of initial ²³⁰Th can be resolved by measurements of local sediments. Results show that carbonate nodules include local sediment as impurities. Furthermore, the results of trace element analyses such as Rb, Zr, Nb, REE, Pb, and Th also support the idea.In all, 18 carbonate samples were dated with correction of initial ²³⁰Th using the mean value of local sediment in this study. The U–Th correction ages show 12–35ka with an isochron age of 26 ± 3ka. Results indicate that during the time interval of U–Th ages, from 12ka to 35ka, environmental conditions must have been favorable for enhanced methane flux through sediment. The extensive methane flow period at 20ka accords with the lowest-stand sea level during the last glacial age. Results of this study also suggest that U–Th ages of carbonate are useful as a reliable chronometer with regard to methane seep activation. In order to acquire U–Th ages of carbonate at methane seep sites, however, it is important to evaluate the amount of initial ²³⁰Th accurately using the value of sediment.     

Dating of Late Pleistocene terrace deposits of the River Rhine using Uranium series and luminescence methods: Potential and limitations

Uranium-series dating of pedogenic carbonate crusts from fluvial gravels is tested using Optically Stimulated Luminescence (OSL) ages as references. OSL dating yielded ages of 30–15 ka and 13–11 ka, which correlate with the cold periods of the Last Glacial Maximum and the Younger Dryas. These ages are internally coherent and consistent with the geological background and are thus regarded as reliable. Most of the U/Th results scatter widely in the ²³⁰Th/²³²Th vs. ²³⁴U/²³²Th isochron diagram, making regression unrealistic. Semiquantitative age estimates from the data were found to be mostly older than the OSL ages and the geological context. It is suggested that a heterogeneous initial ²³⁰Th input, not relatable to a detrital component, is responsible for the observed discrepancies. This input may be due to bacterial activities and Th transport on organic colloids. It appears necessary to avoid samples where bacteria could have contributed to carbonate precipitation. Further, the relative importance of this problem decreases with sample age, so that U/Th dating of sinters is expected to be more reliable in the >100 ka age range.     

Timing of Holocene lake highstands around Dawa Co in inner Tibetan Plateau: Comparison of quartz and feldspar luminescence dating with radiocarbon age

Lakes over the inner Tibetan Plateau (TP) are very sensitive to the regional environmental transformations and climate changes. Well-preserved lake sediments around these lakes provide critical geomorphological and sedimentary evidence that can be used to infer the past hydroclimate changes. In this study, a lacustrine section from a sandy shoreline (∼74 m above the modern lake) situated to the northwest of modern Dawa Co in the inner TP was investigated using both luminescence and radiocarbon dating methods. Our results demonstrated: (1) the quartz optically simulated luminescence (OSL) dating yielded much younger ages (∼4 ka) than that of the post-infrared IRSL (pIRIR) dating of the K-feldspar fraction; (2) fading test showed g-values ranging between 1.34 and 4.46%/decade for quartz OSL signals, which is considered to be responsible for the underestimation of the corresponding ages; (3) the AMS ¹⁴C age of the charcoal sample from the section is in line with the K-feldspar pIRIR₂₂₅ ages, confirming the reliability of the pIRIR₂₂₅ dates and the underestimation of the quartz OSL ages. The anomalous fading of quartz OSL signals and the consequent age underestimation have been reported in several other lakes on the TP, we presented here for the first time firm evidence of the phenomenon with the help of a robust independent control of AMS ¹⁴C age of the charcoal. Based on the pIRIR₂₂₅ and AMS ¹⁴C ages, we conclude that Dawa Co underwent a prominent highstand during the early Holocene (∼9–7 ka), which was probably controlled by the large amounts of glacial meltwater input and the increased monsoonal precipitation.     

Constraining Holocene sea levels using U‐Th ages of phreatic overgrowths on speleothems from coastal caves in Mallorca (Western Mediterranean)

Phreatic overgrowths on speleothems (POS) are carbonate formations deposited at the water table of caves in unique karstic coastal settings having morphologies that can be directly related to sea level at the time of formation. The U‐Th ages of calcite and aragonite overgrowths collected from the modern water table in coastal caves on Mallorca (Cova de Cala Varques A and Cova des Pas de Vallgornera) were determined using high‐precision MC‐ICPMS techniques. U‐Th ages indicate that phreatic carbonate deposition occurred between ca 2·8 and at least 0·6 ka BP and are in accord with an archeologically estimated age of 3·7–3·0 ka BP for a drowned prehistoric construction at a depth of 1 m below current sea level in a cave from the same area. Speleothem δ¹³C and δ¹⁸O and chemical composition of cave pools provide supportive evidence that POS reflect mixing between seawater and brackish water table. Copyright © 2010 John Wiley & Sons, Ltd.     

中国新疆博斯腾湖现代碳库效应研究

碳库效应存在影响了¹⁴C测年的准确性,制约了沉积物在湖泊研究中的应用。本文研究位于典型西风环流带的新疆博斯腾湖现代碳库效应,结合同位素地球化学、水化学等方法,探讨了博斯腾湖碳库效应的影响机制。研究结果表明,博斯腾湖最大现代碳库年龄为3535年,最小为现代碳,集中在670~945年。而过去碳库效应集中在1033~2200年。深水区表现为碳库年龄较小且稳定;在入湖口碳库效应最大,富水生植物浅水区碳库效应最小。与过去碳库年龄相比较,现代碳库效应整体表现更为年轻。研究发现,博斯腾湖口受流域外源“死”碳影响,深水区受湖水与大气CO₂交换率差异影响,富水生植物浅水区可能受水生植物光合作用影响。此外,核爆效应也对博斯腾湖现代碳库效应产生了影响,可能导致最高约1000年的年代误差。利用深水区放射性碳比活度(pMC)平均值与大气碳比活度差值(~18%),得出深水区沉积物存在约846年现代碳库效应,再经核爆效应校正后得出博斯腾湖存在最高约1800年碳库效应。     

Holocene moist period recorded by the chronostratigraphy of a lake sedimentary sequence from Lake Tangra Yumco on the south Tibetan Plateau

Palaeolimnological studies together with geomorphological investigations of exposed lacustrine sections on the Tibetan Plateau provided valuable palaeoclimate records. Radiocarbon dating is the most commonly used method for establishing chronologies of lake sediments. However, ¹⁴C dating of such sediments could be problematic due to the lack of organic matter or a reservoir effect, which commonly appears in radiocarbon ages of lacustrine sediments from the Tibetan Plateau. OSL dating is an alternative for dating the lake sediments and also provides the opportunity to independently test radiocarbon chronologies. The current study tries to compare OSL and ¹⁴C dating results in order to evaluate the reservoir effect of ¹⁴C dating, and then based on quartz OSL dating and stratigraphic analysis, to construct the chronostratigraphy of a lacustrine sedimentary sequence (TYC section), an offshore profile from Tangra Yumco lake on the southern Tibetan Plateau. Results suggest that: (1) it is possible to obtain robust OSL age estimates for these lake sediments and the OSL ages of the three samples range from ca. 7.6 ka to ca. 2.3 ka; (2) The discrepancy between the OSL and ¹⁴C ages is ca. 4–5 ka, which possibly results from the age overestimate of ¹⁴C dating due to a reservoir effect in the studied lake; (3) the chronostratigraphy of TYC section and sedimentological environmental analysis show a large lake with a lake level distinctively above the present during ca. 7.6–2.7 ka indicating a wet mid-Holocene in the study area.     

Seasonal δ13CDIC sourcing and geochemical flux in telogenetic epikarst of south-central Kentucky

Telogenetic epikarst carbon sourcing and transport processes and their associated hydrogeochemical responses are complex and dynamic. Carbon dioxide (CO₂) transport rates in the epikarst zone are often driven by hydrogeochemical responses, which influence carbonate dissolution and conduit formation. This study examines the influence of land use on carbon sourcing and carbonate dissolution kinetics through a comparative analysis of separate, but similar, epikarst systems in south-central Kentucky. The use of high-resolution hydrogeochemical data from multiple data loggers and isotope analysis from collected water samples reflects the processes within these epikarst aquifers, which are estimated to contribute significantly to bedrock dissolution. Results indicate that, in an agricultural setting, long-term variability and dissolution is governed by seasonal production of CO₂ . In a more urbanized, shallower epikarst system, land cover may affect CO₂ transport between the soil and underlying bedrock. This concentration of CO₂ potentially contributes to ongoing dissolution and conduit development, irrespective of seasonality. The observed responses in telogenetic epikarst systems seem to be more similar to eogenetic settings, which is suggested to be driven by CO₂ transport occurring independent of high matrix porosity. The results of this study indicate site-specific responses with respect to both geochemical and δ¹³C_DIC changes on a seasonal scale, despite regional geologic similarities. The results indicate that further comparative analyses between rural and urban landscapes in other karst settings is needed to delineate the impact of land use and seasonality on dissolution and carbon sourcing during karst formation processes. © 2019 John Wiley & Sons, Ltd.     

Mid-Holocene variability in the marine C reservoir age for northern coastal Papua New Guinea

Changes in oceanic radiocarbon (¹⁴C) reservoir ages through the deglaciation and Holocene can provide important information on ocean circulation as Earth's climate warmed. Here, we present reservoir ages for the western tropical Pacific that span the mid-Holocene transition from less to more frequent El Niño events. Reservoir ages were calculated using paired U–Th and conventional ¹⁴C dating of eight individual fossil coral samples from Koil and Muschu Islands, northern coastal Papua New Guinea (PNG). AMS ¹⁴C and MC-ICPMS U–Th dating of additional samples from six of the fossil corals were used to confirm the TIMS U–Th and conventional ¹⁴C ages. The combined results show average reservoir ages of 185±30 ¹⁴C yr (n=4) for 7220–5850 yr BP compared to 420 ¹⁴C yr for a modern coral from Muschu Island. From 5850 to 5420 yr BP reservoir ages increase to modern values. The relatively young reservoir ages from 7220 to 5850 yr BP are best explained by greater influx of well-equilibrated sub-tropical water from the southern branch of the South Equatorial Current (SEC). This is consistent with strengthening trade winds (facilitating air–sea exchange) and a more northerly position of the Intertropical Convergence Zone thought to have occurred at this time. The transition to more modern-like reservoir ages from 5850 to 5420 yr BP suggests modern oceanic circulation patterns were established during this interval. The onset of modern El Niño activity around this time would have served to enhance the intrusion of ¹⁴C-depleted equatorial waters via the south equatorial branch of the SEC. Overall, the changes in reservoir age presented here for the western tropical Pacific suggest that Holocene changes in the El Niño–Southern Oscillation state of the tropical Pacific resulted in reorganisation of oceanic circulation in this region.     

Using the N/C ratio to correct bulk radiocarbon ages from lake sediments: Insights from Chilean Patagonia

The offset between AMS radiocarbon ages obtained on bulk lake sediments and the true age of deposition was evaluated at four sites in Northern Chilean Patagonia. Our results show that the bulk radiocarbon ages are systematically older by 300 to 1100 years. In this region free of carbonate and carbonaceous rocks, we argue that this difference results from variable inputs of terrestrial organic carbon from the Holocene soils that cover the lake watersheds. For the four studied lakes, the age offset is clearly related to the fraction of terrestrial carbon preserved in the lake sediments, which was estimated using the N/C ratio of the bulk organic matter. We propose that N/C measurements can be used to significantly improve chronologies based on radiocarbon dating of bulk lake sediments.     

Calculation of the reservoir age from organic and carbonate fractions of sediments in the Gulf of Cariaco (Caribbean Sea)

A set of 24 AMS ¹⁴C measurements were performed on different sediment fractions from short gravity cores taken from the Gulf of Cariaco (northeastern Venezuela) in order to construct a detailed sedimentary archive for recent centuries. A local reservoir effect was expected because of i) strong upwelling from the neighboring Cariaco Trough and anoxia and ii) the specific geomorphological setting related to active faults with seeps and diapirism. Measurements were thus performed on different components: sediment bulk organic fraction (SBOF), pteropods shells (surface water), bivalve shells (bottom), and plant fragments. Based on comparisons of the different results, we discuss different age corrections and calibrations, which lead us to consider a negligible local reservoir correction (ΔR) for the bivalve and pteropod shells, which show no reservoir age for carbonate and an absence of water stratification. However, a local 633 ± 64 yr ΔR appears in the organic fraction of the sediment, and its origin is primary related to the upwelling mechanism.     

Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.     

CO2-induced dissolution of low permeability carbonates. Part II: Numerical modeling of experiments

We used the 3D continuum-scale reactive transport models to simulate eight core flood experiments for two different carbonate rocks. In these experiments the core samples were reacted with brines equilibrated with pCO₂ = 3, 2, 1, 0.5 MPa (Smith et al., 2013 [27]). The carbonate rocks were from specific Marly dolostone and Vuggy limestone flow units at the IEAGHG Weyburn-Midale CO₂ Monitoring and Storage Project in south-eastern Saskatchewan, Canada. Initial model porosity, permeability, mineral, and surface area distributions were constructed from micro tomography and microscopy characterization data. We constrained model reaction kinetics and porosity–permeability equations with the experimental data. The experimental data included time-dependent solution chemistry and differential pressure measured across the core, and the initial and final pore space and mineral distribution. Calibration of the model with the experimental data allowed investigation of effects of carbonate reactivity, flow velocity, effective permeability, and time on the development and consequences of stable and unstable dissolution fronts.The continuum scale model captured the evolution of distinct dissolution fronts that developed as a consequence of carbonate mineral dissolution and pore scale transport properties. The results show that initial heterogeneity and porosity contrast control the development of the dissolution fronts in these highly reactive systems. This finding is consistent with linear stability analysis and the known positive feedback between mineral dissolution and fluid flow in carbonate formations. Differences in the carbonate kinetic drivers resulting from the range of pCO₂ used in the experiments and the different proportions of more reactive calcite and less reactive dolomite contributed to the development of new pore space, but not to the type of dissolution fronts observed for the two different rock types. The development of the dissolution front was much more dependent on the physical heterogeneity of the carbonate rock. The observed stable dissolution fronts with small but visible dissolution fingers were a consequence of the clustering of a small percentage of larger pores in an otherwise homogeneous Marly dolostone. The observed wormholes in the heterogeneous Vuggy limestone initiated and developed in areas of greater porosity and permeability contrast, following pre-existing preferential flow paths.Model calibration of core flood experiments is one way to specifically constrain parameter input used for specific sites for larger scale simulations. Calibration of the governing rate equations and constants for Vuggy limestones showed that dissolution rate constants reasonably agree with published values. However the calcite dissolution rate constants fitted to the Marly dolostone experiments are much lower than those suggested by literature. The differences in fitted calcite rate constants between the two rock types reflect uncertainty associated with measured reactive surface area and appropriately scaling heterogeneous distribution of less abundant reactive minerals. Calibration of the power-law based porosity–permeability equations was sensitive to the overall heterogeneity of the cores. Stable dissolution fronts of the more homogeneous Marly dolostone could be fit with the exponent n = 3 consistent with the traditional Kozeny–Carman equation developed for porous sandstones. More impermeable and heterogeneous cores required larger n values (n = 6–8).     

Luminescence dating of shoreline sediments indicates a late deglacial lake-level rise of Selin Co on the central Tibetan Plateau

The palaeo-shorelines around the lakes on the Tibetan Plateau can be used to reconstruct water level variations, which serve as sensitive indicators of hydroclimate change. Extensive studies have been carried out to constrain the Holocene lake level fluctuations by dating shorelines with a variety of methods (e.g., luminescence, ¹⁴C, ¹⁰Be and U–Th series). In comparison, the timing of the lake level variations during the last glacial and subsequent deglaciation periods has been rarely studied. The driving factors of such changes, therefore, remain elusive. In this study, we performed a detailed luminescence dating investigation on six samples taken from a nearshore sedimentary outcrop in the south of Selin Co basin. The post-IR IRSL signals measured at 225 °C (pIRIR₂₂₅) on sand-sized K-feldspar grains demonstrated a generally good behavior and yielded reliable chronologies, while the optically stimulated luminescence (OSL) signals of quartz showed systematical age underestimation, which was attributed to anomalous fading. Six pIRIR₂₂₅ ages ranging from 15 to 10 ka suggested that the lake level of Selin Co during the last deglaciation reached up to 40–45 m high above the modern lake level. In view of the regional precipitation and temperature proxy records, we consider that the glacier meltwater supply has likely been the primary contributor to the lake highstands during the last deglaciation.