Revised ΔR values for the Barents Sea and its archipelagos as a pre-requisite for accurate and robust marine-based 14C chronologies

The calibration of marine ¹⁴C dates requires the incorporation of regionally specific marine reservoir offsets known as ΔR, essential for accurate and meaningful inter-archive comparisons. Revised, regional ΔR (‘ΔR_R’) values for the Barents Sea are presented for molluscs and cetaceans for the two latest iterations of the marine calibration curve, based on previously published pre-bomb live-collected and radiocarbon-dated samples (‘ΔR_L’; molluscs: n = 16; cetaceans: n = 18). Molluscan ΔR_R, determined for four broad regional oceanographic settings, are: western Svalbard (including Bjørnøya), −61 ± 37 ¹⁴C yrs (Marine20), 94 ± 38 ¹⁴C yrs (Marine13); Franz Josef Land, −277 ± 57 ¹⁴C yrs (Marine20), −122 ± 38 ¹⁴C yrs (Marine13); Novaya Zemlya, −156 ± 73 ¹⁴C yrs (Marine20), 0 ± 76 ¹⁴C yrs (Marine13); northern Norway, −86 ± 39 ¹⁴C yrs (Marine20), 74 ± 24 ¹⁴C yrs (Marine13). Molluscan ΔR_R values are considered applicable to other marine carbonate materials (e.g., foraminifera, ostracods). Cetacean ΔR_R are determined for toothed (n = 10) and baleen (n = 8) whales, and a combined toothed-baleen group (n = 18): toothed, −161 ± 41 ¹⁴C yrs (Marine20), 1 ± 41 ¹⁴C yrs (Marine13); baleen, −158 ± 43 ¹⁴C yrs (Marine20), 8 ± 41 ¹⁴C yrs (Marine13); combined baleen-toothed whales, −160 ± 41 ¹⁴C yrs (Marine20), 4 ± 49 ¹⁴C yrs (Marine13). Where identification and separation of baleen and toothed whales is impossible the combined ΔR_R term may be used. However, we explicitly discourage the application of existing cetacean ΔR_R terms to other marine mammals. Our new ΔR_R values are applicable for as long as those broad oceanographic conditions (circulation and ventilation) have persisted, i.e., through the Holocene. We recommend using the latest iteration of the marine calibration curve, Marine20, which seems to better capture the time-variant nature of R compared to Marine13. More ΔR_L datapoints for both molluscs and cetaceans would improve the accuracy and precision of ΔR_R. In the meantime, our new ΔR terms facilitate the calibration of marine ¹⁴C dates across the region, paving the way for meaningful and accurate late Quaternary histories and inter-regional comparisons.     

Radiocarbon reservoir corrections on the Brazilian coast from pre-bomb marine shells

Despite the great extent of the Brazilian coast, there are very few studies on the marine radiocarbon reservoir correction local offset (ΔR) for this region.In the present study, we used marine shells from the malacological collection of the National Museum of Brazil to obtain values of ΔR for different locations on the Brazilian coast. According to the museum records, the mollusks were collected alive from the coasts of Rio de Janeiro, Rio Grande do Sul, São Paulo and Bahia, prior to the ¹⁴C bomb-peak. The exact year of collection for each shell is known.The samples were chemically prepared and measured at the Radiocarbon Laboratory of the Universidade Federal Fluminense (LAC-UFF) in Brazil. The conventional ages were calibrated using the Marine13 curve and the ΔR values were calculated using the OxCal software. The values range from 17 ± 56 ¹⁴C yr in São José do Norte, Rio Grande do Sul to 96 ± 48 ¹⁴C yr in Cabo Frio, Rio de Janeiro.     

New marine ΔR values for Arctic Canada

For more than four decades, the reporting of ¹⁴C dates on marine molluscs from Arctic Canada has been notable for the lack of consistently applied marine reservoir corrections. We propose that the common approach of reporting Canadian Arctic marine ¹⁴C dates using presumed time-invariant reservoir corrections be abandoned in favour of calibration of ¹⁴C dates, using the current standard protocol. This approach best facilitates inter- and intra-regional correlation, and correlation with other geochronometers. In order to enable the consistent calibration of marine ¹⁴C dates from Arctic Canada, we analysed a ¹⁴C database of 108 marine mollusc samples collected live between 1894 and 1956, and determined regional reservoir offset values (ΔR) for eight oceanographically distinct regions. The following new ΔR values should be used for ¹⁴C calibration: NW Canadian Arctic Archipelago, 335 ± 85 yrs; Foxe Basin, 310 ± 90 yrs; NE Baffin Island, 220 ± 20 yrs; SE Baffin Island, 150 ± 60 yrs; Hudson Strait, 65 ± 60 yrs; Ungava Bay, 145 ± 95 yrs; Hudson Bay, 110 ± 65 yrs; and James Bay, 365 ± 115 yrs.     

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.     

OSL chronology and accumulation rate of the Nakdong deltaic sediments,southeastern Korean Peninsula

Optically stimulated luminescence (OSL) dating was performed on Late Quaternary deltaic sequences from a 55-m-long core sampled from the Nakdong River estuary, Korea. OSL ages obtained from chemically separated fine (4–11 μm) and coarse (90–212 μm) quartz grains ranged from 29.4 ± 2.6 to 0.4 ± 0.04 ka, revealing clear consistency between the grain-size fractions. The D_e values from the standardized growth curve (SGC) are consistent with those from the single-aliquot regenerative-dose (SAR) procedure, which suggests that the SGC is valid for the Nakdong deltaic sediments. The ¹⁴C ages of shells and wood fragments ranged from 11 to 2.9 ka, demonstrating reasonable agreement with the OSL ages, within the error range. However, the limited number and random sampling interval of the ¹⁴C age data (10 ages) result in a simple linear and exponential trend in the depth–age curve. In contrast, OSL ages obtained by high-resolution sampling show down-section variations in the depth–age curve, indicating the occurrence of rapid changes in sedimentation rate. It is suggested that the high-sampling-resolution OSL ages provide a more realistic and detailed depth–age curve and sedimentation rate. The Nakdong deltaic sediments were divided into five units based on sedimentation rate. The lowest (unit 5) shows a break in sedimentation between the last glacial maximum (LGM) and the Holocene. The sedimentation rate increased in units 4 and 3, presumably corresponding to the early to middle Holocene sea level rise and high stand. Unit 2 shows a gradually decreasing sedimentation rate following the regression of the shoreline, until about 2 ka. The progradation of the Nakdong River delta resulted in the rapid accumulation of unit 1 during the last 2000 years.     

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.     

Differences in stable isotope compositions of freshwater snails from surface sediments of two Polish shallow lakes

The study reports and discusses the differences in δ¹³C and δ¹⁸O values of shells between several species of freshwater snails. Shells were derived from sediment samples collected from depths of 0.5, 1, 2 and 3 m along transects in two shallow eutrophic lakes located in mid-western Poland. Mean δ¹³C values of the shells ranged between −7.5 and −3.8‰ in Lake Jarosławieckie and between −8.1 and −5.2‰ in Lake Rosnowskie Duże, whereas mean δ¹⁸O values ranged between −2.2 and −0.2‰ and between −2.2 and 0.4‰ respectively in the studied lakes. A similar order of species in terms of shell isotope values, from least to most ¹³C and ¹⁸O-depleted was observed in both lakes and seems to indicate constancy of the factors controlling the stable isotope compositions of snail shells. We postulate that the nearly 4‰ difference in the mean carbon stable isotope values between the species was primarily controlled by the amount of metabolic carbon incorporated into the shells and the δ¹³C values of the snail food. Different growth cessation temperatures and microhabitats of the species studied result in temporally and spatially varied DIC δ¹³C values, water δ¹⁸O values and water temperature of shell precipitation, and may thus differentiate the δ¹³C and δ¹⁸O values of shells. The range of δ¹³C and δ¹⁸O values of individual shells from a sediment sample (mean 2.35 and 2.15‰, respectively) is interpreted as reflecting an intraspecific variability of isotope compositions in shells from a population and changes of the ambient conditions during the accumulation of the sediment layer. The species-specificity and intraspecific variability in C and O isotopic compositions of shells allow concluding that in palaeolimnological studies, stable isotope analyses should be performed on a set of mono-specific shells representing mean isotope compositions of the species for the interval studied rather than single shells or multispecific bulk shell material.     

Sources of particulate and dissolved organic carbon in the St Lawrence River: isotopic approach

We investigate sources of both dissolved and particulate organic carbon in the St Lawrence River from its source (the Great Lakes outlet) to its estuary, as well as in two of its tributaries. Special attention is given to seasonal interannual patterns by using data collected on a bi‐monthly basis from mid‐1998 to mid‐2003. δ¹³C measurements in dissolved inorganic carbon, dissolved organic carbon (DOC) and particulate organic carbon (POC), as well as molar C : N in particulate organic matter (POM), are used to bring insight into the dynamic between aquatic versus terrigenous sources. In addition, ¹⁴C activities of DOC were measured at the outlet of the St Lawrence River to its estuary to assess a mean age of the DOC exported to the estuary. In the St Lawrence River itself, aquatically produced POC dominates terrestrially derived POC and is depleted in ¹³C by approximately 12‰ versus dissolved CO₂. In the Ottawa River, the St Lawrence River's most important tributary, the present dataset did not allow for convincing deciphering of POC sources. In a small tributary of the St Lawrence River, aquatically produced POC dominates in summer and terrestrially derived POC dominates in winter. DOC seems to be dominated by terrestrially derived organic matter at all sampling sites, with some influence of DOC derived from aquatically produced POC in summer in the St Lawrence River at the outlet of the Great Lakes and in one of its small tributaries. The overall bulk DOC is relatively recent (¹⁴C generally exceeding 100% modern carbon) in the St Lawrence River at its outlet to the estuary, suggesting that it derives mainly from recent organic matter from topsoils in the watershed. Copyright © 2005 John Wiley & Sons, Ltd.     

Towards radiocarbon calibration beyond 28 ka using speleothems from the Bahamas

We present a new speleothem record of atmospheric Δ¹⁴C between 28 and 44 ka that offers considerable promise for resolving some of the uncertainty associated with existing radiocarbon calibration curves for this time period. The record is based on a comprehensive suite of AMS ¹⁴C ages, using new low-blank protocols, and U–Th ages using high precision MC-ICPMS procedures. Atmospheric Δ¹⁴C was calculated by correcting ¹⁴C ages with a constant dead carbon fraction (DCF) of 22.7 ± 5.9%, based on a comparison of stalagmite ¹⁴C ages with the IntCal04 (Reimer et al., 2004) calibration curve between 15 and 11 ka. The new Δ¹⁴C speleothem record shows similar structure and amplitude to that derived from Cariaco Basin foraminifera (Hughen et al., 2004, 2006), and the match is further improved if the latter is tied to the most recent Greenland ice core chronology (Svensson et al., 2008). These data are however in conflict with a previously published ¹⁴C data set for a stalagmite record from the Bahamas — GB-89-24-1 (Beck et al., 2001), which likely suffered from ¹⁴C analytical blank subtraction issues in the older part of the record. The new Bahamas speleothem ?¹⁴C data do not show the extreme shifts between 44 and 40 ka reported in the previous study (Beck et al., 2001). Causes for the observed structure in derived atmospheric Δ¹⁴C variation based on the new speleothem data are investigated with a suite of simulations using an earth system model of intermediate complexity. Data-model comparison indicates that major fluctuations in atmospheric ?¹⁴C during marine isotope stage 3 is primarily a function of changes in geomagnetic field intensity, although ocean–atmosphere system reorganisation also played a supporting role.     

Total waterborne carbon export and DOC composition from ten nested subarctic peatland catchments—importance of peatland cover,groundwater influence,and inter‐annual variability of precipitation patterns

Waterborne carbon (C) export from terrestrial ecosystems is a potentially important flux for the net catchment C balance and links the biogeochemical C cycling of terrestrial ecosystems to their downstream aquatic ecosystems. We have monitored hydrology and stream chemistry over 3 years in ten nested catchments (0.6–15.1 km²) with variable peatland cover (0%–22%) and groundwater influence in subarctic Sweden. Total waterborne C export, including dissolved and particulate organic carbon (DOC and POC) and dissolved inorganic carbon (DIC), ranged between 2.8 and 7.3 g m^–2 year^–1, representing ~10%–30% of catchment net ecosystem exchange of CO₂. Several characteristics of catchment waterborne C export were affected by interacting effects of peatland cover and groundwater influence, including magnitude and timing, partitioning into DOC, POC, and DIC and chemical composition of the exported DOC. Waterborne C export was greater during the wetter years, equivalent to an average change in export of ~2 g m^–2 year^–1 per 100 mm of precipitation. Wetter years led to a greater relative increase in DIC export than DOC export due to an inferred relative shift in dominance from shallow organic flow pathways to groundwater sources. Indices of DOC composition (SUVA₂₅₄ and a₂₅₀/a₃₆₅) indicated that DOC aromaticity and average molecular weight increased with catchment peatland cover and decreased with increased groundwater influence. Our results provide examples on how waterborne C export and DOC composition might be affected by climate change. Copyright © 2012 John Wiley & Sons, Ltd.     

Atmospheric14C changes resulting from fossil fuel CO2 release and cosmic ray flux variability

A high-precision tree-ring record of the atmospheric¹⁴C levels between 1820 and 1954 is presented. Good agreement is obtained between measured and model calculated 19th and 20th century atmospheric Δ¹⁴C levels when both fossil fuel CO₂ release and predicted natural variations in¹⁴C production are taken into account. The best fit is obtained by using a ?-diffusion model with an oceanic eddy diffusion coefficient of 3 cm²/s, a CO₂ atmosphere-ocean gas exchange rate of 21 moles m^?2 yr^?1 and biospheric residence time of 60 years.For trees in the state of Washington the measured 1949–1951 atmospheric Δ¹⁴C level was20.0±1.2%. below the 1855–1864 level. Model calculations indicate that in 1950 industrial CO₂ emissions are responsible for at least 85% of the Δ¹⁴C decline, whereas natural variability accounts for the remaining 15%.     

Elemental and isotopic signatures of particulate organic carbon in the Zengjiang River,southern China

Riverine total suspended sediment (TSS) at the lower reach section of the Zengjiang River, a low‐turbidity river in the southern China, was sampled on a 4‐week basis from March 2002 to February 2003. The gross TSS was divided into sedimentary and suspended fractions (SED and SUS) by the sedimentation method. Organic carbon and nitrogen, ¹⁴C and ¹³C were analysed using an elemental analyser and accelerator mass spectrometer respectively. The results show that particulate organic carbon (POC) yield is 0·8 × 10⁶ g km^?2 year^?1 in the Zengjiang River drainage basin, which is about one‐tenth of that in the Zhujiang (Pearl) River drainage basin. The C/N ratio demonstrates that aquatic biomass is the major contributor to POC in the Zengjiang River. The average share of aquatic biomass in the SUS‐fraction POC and SED‐fraction POC is about 88·89% and 62·76% respectively, with a substantial seasonal variation. δ¹³C values of SUS‐fraction POC (?26·56 to ? 22·89‰) is slightly lighter than that of SED‐fraction POC (?25·05 to ? 22·20‰), indicating that the contribution of aquatic biomass to δ¹³C values is more pronounced in the SUS‐fraction POC than in the SED‐fraction POC. The ‘bomb’–¹⁴C signature is not detected in the POC of Zengjiang River, and the contribution from geological organic carbon is very little. Δ¹⁴C values of the SED‐fraction POC vary from ? 44 to ? 223‰, and the Δ¹⁴C values of the SUS‐fraction POC vary from ? 33 to ? 165‰. For most paired samples, the SED‐fraction POC is generally more depleted in ¹⁴C than that of its counterpart SUS‐fraction POC. Compared with other small mountainous rivers, the ¹⁴C enrichment of POC in the Zengjiang River indicates slight drainage basin erosion. Copyright © 2006 John Wiley & Sons, Ltd.     

Sediment and trace element depositional history from the Ajkwa River estuarine mangroves of Irian Jaya (West Papua), Indonesia

Radiotracer ²¹⁰Pb and contaminant copper were used to estimate sediment accumulation rates in 4 cores from the Ajkwa River estuary and mangrove tidal channels in western Irian Jaya. Mass accumulation rates (4.5–13 kg dry wt m⁻² yr⁻¹) were within the envelope of expectations for a region of high rainfall, great river catchment relief, and rapid tectonic uplift of mountains. Copper accumulation rates were enhanced 40 fold in surface sediments, compared to pre-1950 sections of the sediment cores. These recent sediments with enhanced copper concentrations come from Freeport Indonesia mine tailings over the last 27 years. Variations in sediment core profiles of Al, Fe, and organic carbon were small, indicating no great change in bulk sediment composition. Sulfur concentrations decline toward the sediment surface, suggesting a decline in rates of microbial sulfate reduction. Enhanced sediment copper concentrations will be a useful tracer of sediment dispersal from the Ajkwa River estuary along this coast.     

Dissolved inorganic nutrients and organic substrates in the River Warnow (North-Eastern Germany) – Utilisation by bacterioplankton

After 1990, external loads of Central European rivers with inorganic nutrients (nitrogen and phosphorus) and organic material were reduced because of changed environmental laws. However, in the eutrophic lowland River Warnow, North-Eastern Germany, nitrate concentrations remained high with 35–185 μmol l⁻¹ without a significant decrease since 1992. In contrast, phosphate concentrations, varying between 0.3 and 5.2 μmol l⁻¹ during the growth season 2002, decreased significantly over the years. However, its concentrations still exceeded 1 μmol l⁻¹ regularly in the growth seasons. This load led to a substantial accumulation of organic matter additional to high terrestrial inputs. Despite the high organic load, the remineralising bacteria were mainly inactive in River Warnow. Therefore, the composition of the dissolved organic material, especially its bioavailability, were investigated during the growth season 2002 and discussed with other potential controlling factors. River Warnow carried a high load of dissolved organic carbon (14 mg l⁻¹), especially of humic substances (5.5 mg C l⁻¹). Bacterial abundance (12×10⁶ ml⁻¹) as well as production (1.7 μg C l⁻¹ h⁻¹) depended on temperature. During late spring and summer at constantly higher temperatures, bacterial production correlated positively to readily utilisable substrates and to humic compounds. Thus, the bacterial community in River Warnow may be well adapted or contain enough species using the available amino acids and carbohydrates as well as humic matter compounds. However, calculated from protozoan biomass, grazing may control bacterial biomass and perhaps community composition profoundly, what lead to the low percentages of active bacteria.     

Closed-system behaviour of the intra-crystalline fraction of amino acids in mollusc shells

When mollusc shells are analysed conventionally for amino acid geochronology, the entire population of amino acids is included, both inter- and intra-crystalline. This study investigates the utility of removing the amino acids that are most susceptible to environmental effects by isolating the fraction of amino acids encapsulated within mineral crystals of mollusc shells (intra-crystalline fraction). Bleaching, heating and leaching (diffusive loss) experiments were undertaken on modern and fossil Corbicula fluminalis, Margaritifera falcata, Bithynia tentaculata and Valvata piscinalis shells. Exposure of powdered mollusc shells to concentrated NaOCl for 48 h effectively reduced the amino acid content of the four taxa to a residual level, assumed to represent the intra-crystalline fraction. When heated in water at 140 °C for 24 h, only 1% of amino acids were leached from the intra-crystalline fraction of modern shells compared with 40% from whole shell. Free amino acids were more effectively retained in the intra-crystalline fraction, comprising 55% (compared with 18%) of the whole shell after 24 h at 140 °C. For fossil gastropods, the inter-shell variability in D/L values for the intra-crystalline fraction of a single-age population was reduced by 50% compared with conventionally analysed shells. In contrast, analysis of the intra-crystalline fraction of C. fluminalis does not appear to improve the results for this taxon, possibly due to variability in shell ultrastructure. Nonetheless, the intra-crystalline fraction in gastropods approximates a closed system of amino acids and appears to provide a superior subset of amino acids for geochronological applications.     

Carbon dioxide,methane, and dissolved carbon dynamics in an urbanized river system

Estimates of greenhouse gas evasion from rivers have been refined over the past decades to constrain their role in global carbon cycle processes. However, despite 55% of the human population living in urban areas, urban rivers have had limited attention. We monitored carbon dynamics in an urbanized river (River Kelvin, 331 km², UK) to explore the drivers of dissolved carbon lateral and vertical export. Over a 2-year sampling period, riverine methane (CH₄) and carbon dioxide (CO₂) concentrations were consistently oversaturated with respect to atmospheric equilibria, leading to continual degassing to the atmosphere. Carbon stable isotopic compositions (δ¹³C) indicated that terrestrially derived carbon comprised most of the riverine CH₄ and dissolved CO₂ (CO₂*) load while dissolved inorganic carbon (DIC) from groundwater was the main form of riverine DIC. The dynamics of CH₄, CO₂*, and DIC in the river were primarily hydrology-controlled, that is, [CH₄] and [CO₂*] both increased with elevated discharge, total [DIC] decreased with elevated discharge while the proportion of biologically derived DIC increased with increasing discharge. The concentration of dissolved organic carbon (DOC) showed a weak relationship with river hydrology in summer and autumn and was likely influenced by the combined sewer overflows. Carbon emission to the atmosphere is estimated to be 3.10 ± 0.61 kg C·m⁻²·yr⁻¹ normalized to water surface area, with more than 99% emitted as CO₂. Annual carbon loss to the coastal estuary is approximately 4.69 ± 0.70 Gg C yr⁻¹, with annual DIC export approximately double that of DOC. Per unit area, the River Kelvin was a smaller carbon source to the atmosphere than natural rivers/streams but shows elevated fluxes of DIC and DOC under comparable conditions. This research illustrates the role urban systems may have on riverine carbon dynamics and demonstrates the potential tight link between urbanization and riverine carbon export.     

Carbon isotope fractionation of dissolved inorganic carbon (DIC) due to outgassing of carbon dioxide from a headwater stream

The stable isotopic composition of dissolved inorganic carbon (δ¹³C‐DIC) was investigated as a potential tracer of streamflow generation processes at the Sleepers River Research Watershed, Vermont, USA. Downstream sampling showed δ¹³C‐DIC increased between 3–5‰ from the stream source to the outlet weir approximately 0·5 km downstream, concomitant with increasing pH and decreasing PCO₂. An increase in δ¹³C‐DIC of 2·4 ± 0·1‰ per log unit decrease of excess PCO₂ (stream PCO₂ normalized to atmospheric PCO₂) was observed from downstream transect data collected during snowmelt. Isotopic fractionation of DIC due to CO₂ outgassing rather than exchange with atmospheric CO₂ may be the primary cause of increased δ¹³C‐DIC values downstream when PCO₂ of surface freshwater exceeds twice the atmospheric CO₂ concentration. Although CO₂ outgassing caused a general increase in stream δ¹³C‐DIC values, points of localized groundwater seepage into the stream were identified by decreases in δ¹³C‐DIC and increases in DIC concentration of the stream water superimposed upon the general downstream trend. In addition, comparison between snowmelt, early spring and summer seasons showed that DIC is flushed from shallow groundwater flowpaths during snowmelt and is replaced by a greater proportion of DIC derived from soil CO₂ during the early spring growing season. Thus, in spite of effects from CO₂ outgassing, δ¹³C of DIC can be a useful indicator of groundwater additions to headwater streams and a tracer of carbon dynamics in catchments. Copyright © 2007 John Wiley & Sons, Ltd.     

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.     

Geochemical evidence for non-marine depositional environment of foraminiferal fossils from the Nihewan Basin, China

From the first finding in 1970s, the findings of foraminiferal fossil assemblages in inland basins have been reported from time to time, especially in recent years. The debates on the depositional environment of foraminiferal fossils have become the hot spot of researches again in China. Based on the researches of trace element geochemistry and electron scanning microscope of shells of Quaternary foraminiferal fossils from the Xiaodukou section in the inland Nihewan basin, the original ⁸⁷Sr/⁸⁶Sr and other geochemical information of shells were believed to be preserved well and could be used to rebuild the geochemistry of contemporary waters where foraminifera deposited, although there existed some effects of burial diagenesis on the geochemistry of shells to a certain extent. The ⁸⁷Sr/⁸⁶Sr ratios of well-preserved Xiaodukou foraminiferal shells were measured, giving a range of 0.711190±25–0.712018±14, apparently higher than the value of contemporary seawater (0.709087–0.709147) and similar to that of the Sanggan River, proving that it represented the value of the ancient lacustrine water. The hyperbolic mixing models of ⁸⁷Sr/⁸⁶Sr-palaeosalinity and ⁸⁷Sr/⁸⁶Sr-Sr/Ca indicated that the contemporary waters where Xiaodukou foraminifera inhabited was an inland lake and there was no seawater input to the depositional environment.     

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.