Tracing dissolved O2 and dissolved inorganic carbon stable isotope dynamics in the Nyack aquifer: Middle Fork Flathead River, Montana, USA

The geochemistry and microbiology of shallow groundwater aquifers is greatly influenced by the concentration of dissolved oxygen gas (DO); however, the mechanisms that consume DO in groundwater (e.g., biotic or abiotic) are often ambiguous. The use of stable isotopes of molecular O₂ (δ¹⁸O-DO), in conjunction with stable isotopes of dissolved inorganic carbon (δ¹³C-DIC), has potential to discriminate between the various mechanisms causing DO depletion in subsurface waters.Here we report the results of spatial and seasonal changes in δ¹⁸O-DO and δ¹³C-DIC at the Nyack floodplain aquifer along the Middle Fork of the Flathead River near West Glacier, Montana, USA. Over a short, well constrained flow path (∼100 m) near a main recharge zone of the floodplain, the δ¹⁸O-DO consistently increased as DO concentrations decreased with distance from the recharge source. Concurrently, DIC concentrations increased and δ¹³C-DIC values decreased. These observations are explained by community respiration coupled with dissolution of calcite from cobbles in the aquifer matrix. When these results are compared to data from wells distributed over the entire floodplain (several km) a much less predictable relationship was observed between DO concentration and δ¹⁸O-DO. Many wells with low DO concentrations (e.g., <125 μmol L⁻¹ or 4 mg L⁻¹) had anomalously low δ¹⁸O-DO values (e.g., <20‰). Mass balance calculations show that approximately equal amounts of O₂ may be contributed to the aquifer by diffusion from the vadose zone and by advection from the river recharge. Calculations presented here suggest that diffusion across a narrow air-water interface can contribute isotopically light δ¹⁸O-DO to the saturated zone. Possible contributions of light δ¹⁸O-DO from other processes, such as isotopic exchange and radial oxygen loss from plant roots in or near the water table, are compared and evaluated.     

Assessment of diel chemical and isotopic techniques to investigate biogeochemical cycles in the upper Klamath River,Oregon, USA

The upper Klamath River experiences a cyanobacterial algal bloom and poor water quality during the summer. Diel chemical and isotopic techniques have been employed in order to investigate the rates of biogeochemical processes.Four diel measurements of field parameters (temperature, pH, dissolved oxygen concentrations, and alkalinity) and stable isotope compositions (dissolved oxygen–δ¹⁸O and dissolved inorganic carbon–δ¹³C) have been performed between June 2007 and August 2008. Significant diel variations of pH, dissolved oxygen (DO) concentration, and DO–δ¹⁸O were observed, due to varying rates of primary productivity vs. respiration vs. gas exchange with air. Diel cycles are generally similar to those previously observed in river systems, although there are also differences compared to previous studies. In large part, these different diel signatures are the result of the low turbulence of the upper Klamath River. Observed changes in the diel signatures vs. sampling date reflect the evolution of the status of the algal bloom over the course of the summer.Results indicate the potential utility of applying diel chemical and stable isotope techniques to investigate the rates of biogeochemical cycles in slow-moving rivers, lakes, and reservoirs, but also illustrate the increased complexity of stable isotope dynamics in these low-turbulence systems compared to well-mixed aquatic systems.     

Behavior of stable isotopes of dissolved oxygen,dissolved inorganic carbon and nitrate in groundwater at a former wood treatment facility containing hydrocarbon contamination

The speciation and mobility of a variety of chemical species in groundwater are strongly influenced by redox and pH conditions. Dissolved O₂ (DO) and dissolved inorganic C (DIC) concentrations are significant controls of these conditions, respectively. It is not always clear what the major processes are that influence changes in the concentration of DO and DIC across a groundwater flowpath. The combined use of the stable isotope compositions of DO (δ¹⁸O–DO) and DIC (δ¹³C–DIC) has the potential to help investigators discriminate between sources and sinks of DO and DIC in groundwater systems.     

Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining

Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles.Average δ⁶⁶Zn and δ⁶⁵Cu values for streams varied from +0.02‰ to +0.46‰ and −0.7‰ to +1.4‰, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ∼0.3‰ (^66/64Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales.     

Stable isotope composition of CO2 outgassed from cores of argillites: a simple method to constrain δ18O of porewater and δ13C of dissolved carbon in mudrocks

Stable isotope characterization of porewater, and dissolved species, in mudrocks and argillaceous rocks is notoriously difficult. Techniques based on physical or chemical extraction of porewater can generate significant analytical artefacts. The authors report a novel, simple approach to determine the δ¹⁸O of porewater and δ¹³C of dissolved C in argillites. The method uses core samples placed in specifically-designed outgassing cells, sealed shortly after drilling and stored in well-controlled conditions. After 1–2 months, CO₂ naturally outgassed by argillite porewater is collected, purified and analyzed for C and O isotopes. Porewater δ¹⁸O and dissolved C δ¹³C are calculated from CO₂ isotope data using appropriate fractionation factors. This methodology was successfully applied to the Callovo-Oxfordian argillites from Bure (eastern Paris Basin, France) and the Opalinus Clay formation from Mont Terri (Switzerland). In both clay formations, results indicate that porewater is meteoric and dissolved C is of marine origin. The main advantage of the approach is that it does not induce any major physical or chemical disturbance to the clay–water system investigated. Further testing on argillaceous rocks of variable composition and organic content is needed to assess extent of applicability.     

Amino acid nitrogen isotopic fractionation patterns as indicators of heterotrophy in plankton, particulate, and dissolved organic matter

Bulk nitrogen (N) isotope signatures have long been used to investigate organic N source and food web structure in aquatic ecosystems. This paper explores the use of compound-specific δ¹⁵N patterns of amino acids (δ¹⁵N-AA) as a new tool to examine source and processing history in non-living marine organic matter. We measured δ¹⁵N-AA distributions in plankton tows, sinking particulate organic matter (POM), and ultrafiltered dissolved organic matter (UDOM) in the central Pacific Ocean. δ¹⁵N-AA patterns in eukaryotic algae and mixed plankton tows closely resemble those previously reported in culture. δ¹⁵N differences between individual amino acids (AA) strongly suggest that the sharply divergent δ¹⁵N enrichment for different AA with trophic transfer, as first reported by [McClelland, J.W. and Montoya, J.P. (2002) Trophic relationships and the nitrogen isotopic composition of amino acids. Ecology83, 2173-2180], is a general phenomenon. In addition, differences in δ¹⁵N of individual AA indicative of trophic transfers are clearly preserved in sinking POM, along with additional changes that may indicate subsequent microbial reworking after incorporation into particles.We propose two internally normalized δ¹⁵N proxies that track heterotrophic processes in detrital organic matter. Both are based on isotopic signatures in multiple AA, chosen to minimize potential problems associated with any single compound in degraded materials. A trophic level indicator (ΔTr) is derived from the δ¹⁵N difference between selected groups of AA based on their relative enrichment with trophic transfer. We propose that a corresponding measure of the variance within a sub-group of AA (designated ΣV) may indicate total AA resynthesis, and be strongly tied to heterotrophic microbial reworking in detrital materials. Together, we hypothesize that ΔTr and ΣV define a two dimensional trophic “space”, which may simultaneously express relative extent of eukaryotic and bacterial heterotrophic processing.In the equatorial Pacific, ΔTr indicates an average of 1.5-2 trophic transfers between phytoplankton and sinking POM at all depths and locations. The ΣV parameter suggests that substantial variation may exist in bacterial heterotrophic processing between differing regions and time periods. In dissolved material δ¹⁵N-AA patterns appear unrelated to those in POM. In contrast to POM, δ¹⁵N-AA signatures in UDOM show no clear changes with depth, and suggest that dissolved AA preserved throughout the oceanic water column have undergone few, if any, trophic transfers. Together these data suggest a sharp divide between processing histories, and possibly sources, of particulate vs. dissolved AA.     

Tracing the decomposition of dissolved organic carbon in artificial groundwater recharge using carbon isotope ratios

Reducing the concentration of dissolved organic C (DOC) in water is one of the main challenges in the process of artificial groundwater recharge. At the Tuusula waterworks in southern Finland, surface water is artificially recharged into an esker by pond infiltration and an equal amount of groundwater is daily pumped from the aquifer. This groundwater study was conducted to consider the role of redox processes in the decomposition of DOC. The isotopic composition of dissolved inorganic C (δ¹³C_DIC) in the recharged water was used as a tracer for redox reactions. The isotopic composition of O and H in water was determined in order to calculate mixing ratios between the local groundwater and the infiltrated surface water. Three distinct processes in the reduction of the DOC content were traced using isotopic methods and concentration analyses of DIC and DOC: (1) the decomposition of DOC, (2) adsorption of DOC on mineral matter, and (3) the dilution of artificially recharged water by mixing with local groundwater. The largest decrease (44%) in the DOC content occurred during the early stage of subsurface flow, within 350 m of the infiltration ponds. The reduction of DOC was accompanied by an equal increase in DIC and a significant drop in δ¹³C_DIC. This change is attributed to the oxidative decomposition of DOC. A further 23% decrease in DOC is attributed to adsorption and a final drop of 14% to dilution with local groundwater.     

水生植物对岩溶区河水地球化学昼夜变化的影响——以漓江为例

为研究河流非岩溶区断面和岩溶区断面生物地球化学昼夜变化过程、特征及影响因素,探讨水生生物对岩溶区河水碳汇作用的影响,于2016年10月30日-2016年11月1日,在广西桂林漓江干流非岩溶区的峡背和岩溶区的省里设置两个监测点同时开展了为期48小时的高分辨率在线监测和高频率取样工作,研究其水文参数(电导率(EC)、水温(T)、pH以及Ca2+、HCO-3、NO-3等离子和溶解无机碳同位素(δ13CDIC)等水化学参数的昼夜变化规律,并分析其影响因素。发现:（1）峡背和省里两断面水化学类型为HCO3－Ca型,但水文地球化学昼夜变化过程不同:省里断面的物理化学参数昼夜变化显著,T、pH、DO、SIC白天上升夜间下降,Ca2+、HCO-3的质量浓度和EC、p (CO2)白天降低、夜晚上升;而峡背断面理化指标昼夜变幅小,这与峡背断面处于岩溶区与非岩溶区交界处,非岩溶河流汇入、生物量较小等环境特征有关。（2）省里断面营养元素(NO-3、SO42-、Cl-、Na+)昼夜变化过程主要受水生植物同化作用控制,呈现白天降低、夜间升高的变化规律。（3）峡背断面和省里断面TOC 与DOC白天上升、夜间下降,最高日变化幅度可达79%和61%,利用端元混合模型计算得出省里断面和峡背断面内源有机碳占总有机碳的比例分别为91.99%和88.39%,省里断面和峡背断面水生植物光合作用利用HCO-3作为无机碳源的比例为67.42%～99.75%和57.76%～69.78%,平均值分别为79.54%和63.13%。（4）省里断面溶解无机碳(DIC)变化范围为67.1～115.9 mg·L-1,平均值为96.5 mg·L-1,呈现白天下降夜间上升的变化。δ13CDIC变化范围-7.8‰～-9.9‰,平均值为-8.9‰,表现为白天偏重、晚上偏轻的动态变化,两者呈显著的负相关关系(相关系数为-0.79)。研究表明省里断面水生植物光合作用和呼吸作用以及钙沉降是控制DIC昼夜变化的主导因素。通过估算监测期间省里断面光合作用DIC转化速率平均值为1.2×10-5 mmol·L-1·S-1,Ca2+离子的沉积速率平均值为0.18×10-5mmol·L-1·S-1。因此,岩溶区河段水生生物光合作用及其固碳能力较非岩溶区河段明显增强。      

Chemical weathering processes in the Yalong River draining the eastern Tibetan Plateau,China

To better understand chemical weathering and controlling processes in the Yalong River of the eastern Tibetan Plateau, this study presents major ion concentrations and stable isotopes of the dissolved loads. The isotopic compositions (δ¹³C-DIC, δ³⁴S and δ¹⁸O-SO₄) of the dissolved loads are very useful to quantify solute sources and define the carbon budget related with chemical weathering in riverine systems. The isotopic composition of sulphate demonstrates that most of the sulphate is derived from sulphide oxidation, particularly in the upper reach of the Yalong River. The correlations between δ¹³C-DIC, water chemistry and isotopes of sulphate, suggest that the carbon dynamics are mainly affected by carbonate weathering by sulphuric acid and equilibration processes. Approximately 13% of the dissolved inorganic carbon in the Yalong River originates from carbonate weathering by strong acid. The CO₂ consumption rates are estimated to be 2.8 × 10⁵ mol/km²/yr and 0.9 × 10⁵ mol/km²/yr via carbonate and silicate weathering in the Yalong River, respectively. In this study, the influence of sulphide oxidation and metamorphic CO₂ on the carbon budget is estimated for the Yalong River draining the eastern Tibetan Plateau.     

Carbon and oxygen isotope study of the active water-carbonate system in a karstic Mediterranean cave: Implications for paleoclimate research in semiarid regions

In a semiarid climatic zone, such as the Eastern Mediterranean region, annual rainfall variations and fractionation processes in the epikarst zone exert a profound influence on the isotopic compositions of waters seeping into a cave. Consequently, the isotopic compositions of speleothems depositing from cave waters may show complex variations that need to be understood if they are to be exploited for paleoclimate studies. This is confirmed by a four-year study of the active carbonate-water system in the Soreq cave (Israel). The δ¹⁸O (SMOW) values of cave waters range from −6.3 to −3.5%.. The highest δ¹⁸O values occur at the end of the dry season in waters dripping from stalactites, and reflect evaporation processes in the epikarst zone, whereas the lowest values occur in rapidly dripping (fast-drip) waters at the peak of the rainy seasons. However, even fast-drip waters are about 1.5%. heavier than the rainfall above the cave, which is taken to reflect the mixing of fresh with residual evaporated water in the epikarst zone. δ¹³C (PDB) values of dissolved inorganic carbon (DIC) vary from −15.6 to −5.4%., with fast-drip waters having lower δ¹³C values (mostly −15.6 to −12%.) and higher DIC concentrations relative to pool and stalactite-drip water. The low δ¹³C values of fast-drip waters and their supersaturation with respect to calcium carbonate indicates that the seepage waters have dissolved both soil-CO₂ derived from overlying C₃-type vegetation and marine dolomite host rock.The δ¹⁸O (PDB) values of various types of present-day low-magnesium calcite (LMC) speleothems range from −6.5 to −4.3%. and δ¹³C values from −13 to −5.5%. and are not correlated with speleothem type. An analysis of δ¹⁸O values of present-day calcite rafts and pool waters shows that they form in oxygen isotope equilibrium. Similarly, the measured ranges of δ¹³C and δ¹⁸O values for all types of present-day speleothems are consistent with equilibrium deposition at cave temperatures. The δ¹³C–δ¹⁸O range of contemporary LMC thus reflects the variations in temperatures and isotopic compositions of the presentday cave waters. The 10%. variation in the δ¹³C values in waters can be modeled by a simple Rayleigh calculation of the carbon isotope fractionation accompanying CO₂-degassing and carbonate precipitation. These variations may obscure the differences in the carbon isotopic composition of speleothems that could arise when vegetation cover changes from C₃ to C₄-type plants. This consideration emphasizes that it is necessary to characterize the full range of δ¹³C values associated with contemporaneous speleothems in order to clarify the effects of degassing from those due to differing vegetation types.Isotopic studies of a number of different types of fossil LMC speleothems show many of them to exhibit isotopic trends that are similar to those of present-day LMC, but others show both higher and lower δ¹⁸O ranges. In particular, the higher δ¹⁸O range has been shown by independent age-measurements to be associated with a period of drier conditions. The results of the study thus indicate that it is necessary to work on a well calibrated cave system in semiarid climates and that the fossil speleothem record should be obtained from different types of contemporaneous deposit in order to fully characterize the δ¹⁸O–δ¹³C range representative of any given climatic period.     

Thermal analysis (TG–DTA) and isotopic characterization (13C–15N) of humic acids from different origins

Thermal analyses (TG–DTA), elemental composition and isotope analyses (¹³C and ¹⁵N) were performed on humic acids (HA) from peats, leonardites and lignites, in order to investigate their structure and the changes taking place during the humification process. Thermal analyses showed structural differences between HA samples in relation to their coalification rank. In particular the lignite HA were characterized by a more stable chemical composition at high temperatures.The δ¹³C and δ¹⁵N values can provide information on the biogeochemical processes involved in HA formation. In particular, peat HA were linked to anoxic environments that enable plant residues to persist in their structure. In contrast, leonardite and lignite HA formation seems to be governed by different biogeochemical processes from those responsible for peat diagenesis. However, the isotopic analyses did not provide any distinction between leonardite and lignite HA. On the basis of the data presented in this study, it may be concluded that TG–DTA and isotope ratio measurements are powerful tools for investigating the formation pathway of humic substances from coals.     

Development of climatic and vegetation conditions and the geochemical and isotopic composition in the Franconian Albvorland aquifer system

The impact of climatic and vegetation conditions over the past 15 Ka on the chemical composition and ¹⁴C dating of groundwater from the Franconian Albvorland aquifer system is discussed. Seven groundwaters over a flow distance of 25.5 km are investigated. Groundwater dating is made by ¹⁴C of dissolved inorganic carbon (DIC) and aqueous fulvic acid as well as ¹⁸O. ¹⁴C dating via fulvic acid gives groundwater ages consistent with climatic and vegetation records and variations in the groundwater composition. No correction for geochemical processes is required, since under these geochemical conditions fulvic acid remains stable over this time period and flow-distance. On the other hand, ¹⁴C dating via DIC requires correction of the ¹⁴C value due to perturbation by different geochemical processes. Up to a groundwater flow distance of approximately 17 km and an age of about 10 Ka, the ¹⁴C dating by DIC shows considerable dependence on the ¹⁴C-correction model applied. Beyond this groundwater age, ¹⁴C-DIC dating results in an overestimation by two to three ¹⁴C half-lives (T_1/2=5730 a). This deviation may result from different groundwater recharge conditions at the end of the past glaciation and geochemical processes acting on DIC that cannot be adequately characterized. The present study has implications for humic substance mediated transport of pollutants in natural aquatic systems over long time periods.     

Seasonal water-column dynamics of dissolved inorganic carbon stable isotopic compositions (δCDIC) in small hardwater lakes in Minnesota and Montana

The carbon stable isotopic value of dissolved inorganic carbon (δ¹³C_DIC) was measured over several years at different depths in the water column in six carbonate-precipitating temperate lakes. δ¹³C_DIC behavior in three of these lakes departed from the conventional model wherein epilimnetic waters are seasonally enriched relative to all hypolimnetic waters, and in general δ¹³C_DIC values in the water column were not readily correlated to parameters such as lake stratification, algal productivity, hydraulic residence time, or water chemistry. Additionally, the processes implicated in generating the δ¹³C_DIC values of individual lakes differ between lakes with similar δ¹³C_DIC compositions. Each lake thus initially appears idiosyncratic, but when the effects of carbonate mineral equilibria, microbial activity, and lake residence time are viewed in terms of the magnitude of distinct DIC pools and fluxes in stratified lakes, generalizations can be made that allow lakes to be grouped by δ¹³C_DIC behavior. We recognize three modes in the relationship between δ¹³C_DIC values and DIC concentration ([DIC]) of individual lakes: (A) δ¹³C_DIC values decreasing with increasing [DIC]; (B) δ¹³C_DIC values increasing with increasing [DIC]; (C) δ¹³C_DIC values decreasing with increasing [DIC] but increasing again at the highest [DIC]. This approach is useful both in understanding δ¹³C_DIC dynamics in modern hardwater lakes and in reconstructing the environmental changes recorded by sedimentary δ¹³C components in the lacustrine paleorecord.     

Temporal Variability in the Concentration and Stable Carbon Isotope Composition of Dissolved Inorganic and Organic Carbon in Two Montana,USA Rivers

Here we report diel (24 h) and seasonal differences in the concentration and stable carbon isotope composition of dissolved inorganic (DIC) and organic carbon (DOC) in the Clark Fork (CFR) and Big Hole (BHR) Rivers of southwestern Montana, USA. In the CFR, DIC concentration decreased during the daytime and increased at night while DOC showed an inverse temporal relationship; increasing in the daytime most likely due to release of organic photosynthates and decreasing overnight due to heterotrophic consumption. The stable isotope composition of DIC (δ¹³C-DIC) became enriched during the day and depleted over night and the δ¹³C-DOC displayed the inverse temporal pattern. Additionally, the night time molar rate of decrease in the concentration of DOC was up to two orders of magnitude smaller than the rate of increase in the concentration of DIC indicating that oxidation of DOC was responsible for only a small part of the increase in inorganic carbon. In the BHR, in two successive years (late summer 2006 & 2007), the DIC displayed little diel concentration change, however, the δ¹³C-DIC did show a more typical diel pattern characteristic of the influences of photosynthesis and respiration indicating that the isotopic composition of DIC can change while the concentration stays relatively constant. During 2006, a sharp night time increase in DOC was measured; opposite to the result observed in the CFR and may be related to the night time increase in flow and pH also observed in that year. This night time increase in DOC, flow, and pH was not observed 1 year later at approximately the same time of year. An in-stream mesocosm chamber used during 2006 showed that the night time increase in pH and DOC did not occur in water that was isolated from upstream or hyporheic contributions. This result suggests that a “pulse” of high DOC and pH water was advected to the sampling site in the BHR in 2006 and a model is proposed to explain this temporal pattern.     

Diel biogeochemical cycling in a hyperventilating shallow estuarine environment

A diel biogeochemical study was performed to assess the influence that periods of elevated biological activity have on the biogeochemical cycling of macronutrients and redox-sensitive elements in a natural estuarine environment. High-resolution data (15 min sampling) illustrates periodic extreme variations in dissolved oxygen (DO) in the shallow waters of Azevedo Pond, Elkhom Slough, California. During periods of low tidal flushing, DO values can range from highly oxic (>560 μM O₂: >250% saturation) during sunny days to suboxic conditions (<5 μM) at night. Nutrient cycling and redox-sensitive trace element biogeochemistry were evaluated in response to the extreme daily DO fluctuations. A diel sampling study was conducted over a 26-h period, where O₂ concentrations ranged from 346 μM to sustained non-detectable levels in the night hours. In concert with the DO fluctuations, diel phosphate cycling was on the order of 4 μM in response to tidal flushing events and biological assimilation and regeneration. The IO₃ ⁻/I⁻ redox couple quickly responded to suboxic conditions in the water column by a marked increase in I⁻ concentrations and corresponding depletion of IO₃ ⁻. The extreme fluctuations of the p∈ in the water column resulted in diel dissolved Mn²⁺ variations of nearly 5 μM, with observed dissolved Mn removal rates on the order of 1 μM h⁻¹. The elevated biogeochemical cycling of oxygen, nitrogen, phosphorus, iodine, manganese, and iron found in this shallow estuarine environment suggest that tidal restrictions and anthropogenic nutrient enrichments can amplify diel variations and potentially hinder the functional and ecological stability of these systems. These data suggest that accurate chemical monitoring of the health of an estuarine ecosystem must account for the diel variability inherent in these highly productive environments.     

Variability of Stable Isotope Fingerprints of the Serpulid Ficopomatus enigmaticus Within a Permanently Stratified Estuary: Implications for (Palaeo)environmental Interpretations

This paper examines how the mixing of freshwater and seawater, and related mixing of freshwater and marine particulate organic matter (POM) in the permanently stratified estuary of the River Krka, Croatia, are reflected in the stable isotope fingerprints of soft tissues and tubes of the serpulid Ficopomatus enigmaticus. The carbon stable isotope composition (δ¹³C values) of the river-borne POM is retained over long distances, causing a depletion in ¹³C of POM in brackish waters. A trophic depletion in ¹³C was recorded in serpulid soft tissues. The serpulid carbonate tubes were depleted in ¹³C even at locations with salinity close to that of the sea and were subject to large isotope fractionation between dissolved inorganic C (DIC) and carbonate caused by vital effects, making carbonate depleted in ¹³C by several per mil compared with DIC. These effects, though large in the freshwater zone, fade towards the sea. The carbonate δ¹⁸O values of tubes reflect the δ¹⁸O values of the water. The temperature-related differences in δ¹⁸O values of tubes from different sites are masked by source-related differences in the δ¹⁸O values of water arising from mixing of freshwater and seawater in the estuary. Therefore, in serpulide tubes, the terrestrial component can easily be overestimated because of vital effects during biomineralisation and trophic depletion in ¹³C in freshwater and brackish environments.     

The stable carbon isotope biogeochemistry of acetate and other dissolved carbon species in deep subseafloor sediments at the northern Cascadia Margin

Ocean drilling has revealed the existence of vast microbial populations in the deep subseafloor, but to date little is known about their metabolic activities. To better understand the biogeochemical processes in the deep biosphere, we investigate the stable carbon isotope chemistry of acetate and other carbon-bearing metabolites in sediment pore-waters. Acetate is a key metabolite in the cycling of carbon in anoxic sediments. Its stable carbon isotopic composition provides information on the metabolic processes dominating acetate turnover in situ. This study reports our findings for a methane-rich site at the northern Cascadia Margin (NE Pacific) where Expedition 311 of the Integrated Ocean Drilling Program (IODP) sampled the upper 190 m of sediment. At Site U1329, δ¹³C values of acetate span a wide range from −46.0‰ to −11.0‰ vs. VPDB and change systematically with sediment depth. In contrast, δ¹³C values of both the bulk dissolved organic carbon (DOC) (−21.6 ± 1.3‰ vs. VPDB) and the low-molecular-weight compound lactate (−20.9 ± 1.8‰ vs. VPDB) show little variability. These species are interpreted to represent the carbon isotopic composition of fermentation products. Relative to DOC, acetate is up to 23.1‰ depleted and up to 9.1‰ enriched in ¹³C. Broadly, ¹³C-depletions of acetate relative to DOC indicate flux of carbon from acetogenesis into the acetate pool while ¹³C-enrichments of pore-water acetate relative to DOC suggest consumption of acetate by acetoclastic methanogenesis. Isotopic relationships between acetate and lactate or DOC provide new information on the carbon flow and the presence and activity of specific functional microbial communities in distinct biogeochemical horizons of the sediment. In particular, they suggest that acetogenic CO₂-reduction can coexist with methanogenic CO₂-reduction, a notion contrary to the hypothesis that hydrogen levels are controlled by the thermodynamically most favorable electron-accepting process. Further, the isotopic relationship suggests a relative increase in acetate flow to acetoclastic methanogenesis with depth although its contribution to total methanogenesis is probably small. Our study demonstrates how the stable carbon isotope biogeochemistry of acetate can be used to identify pathways of microbial carbon turnover in subsurface environments. Our observations also raise new questions regarding the factors controlling acetate turnover in marine sediments.     

Isotope evidence for quantifying river evaporation and recharge processes in the lower reaches of the Yellow River

Evaporation and recharge are important hydrological processes in the water cycle. However, accurately quantifying these two processes of river remains to be difficult due to their spatial heterogeneity and the limitations of traditional methods. In this study, a more reliable method of stable isotopes of δ ¹⁸O and δ ²H based on the Rayleigh distillation equation and mass conservation was used to estimate the evaporation and recharge of the rivers in the lower reaches of the Yellow River, North China Plain. Comprehensive sampling campaigns including 30 surface water samples from 10 rivers, 33 groundwater samples from domestic and observation wells, and two Yellow River water samples were conducted. The results showed that the evaporation proportion of the rivers based on δ ¹⁸O and δ ²H both averaged 14.4%. The evaporation proportions in each river did not completely follow a linear increasing trend along the flow path. This phenomenon could be mainly explained by the different proportions of recharge from groundwater and Yellow River water. With closer to the Yellow river, evaporation of the rivers decreased while the recharge by the Yellow River increased. Regression equations based on δ ¹⁸O, δ ²H, and their average revealed that the evaporation proportion respectively increased by 1.02, 0.79, and 0.90% with the increase in the distance to the Yellow River per 10 km. On the contrary, the recharge proportion decreased by 7.68, 5.51, and 6.59%, respectively. In addition, using δ ¹⁸O rather than δ ²H was more reliable in studying the spatial influence of the Yellow River on evaporation and recharge. Sensitivity analysis showed that the evaporation model was most sensitive to isotopic composition, rather than to air temperature or relative humidity. The results of this study provide insights into the determination of river hydrological processes and the management of water resources.     

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.