Origin and chemical and isotopic evolution of dissolved inorganic carbon (DIC) in groundwater of the Okavango Delta,Botswana

The origin and the chemical and isotopic evolution of dissolved inorganic carbon (DIC) in groundwater of the Okavango Delta in semi-arid Botswana were investigated using DIC and major ion concentrations and stable oxygen, hydrogen and carbon isotopes (δD, δ¹⁸O and δ¹³C_DIC). The δD and δ¹⁸O indicated that groundwater was recharged by evaporated river water and unevaporated rain. The river water and shallow (<10 m) groundwater are Ca–Na–HCO₃ type and the deep (≥10 m) groundwater is Na–K–HCO₃ to HCO₃–Cl–SO₄ to Cl–SO₄–HCO₃. Compared to river water, the mean DIC concentrations were 2 times higher in shallow groundwater, 7 times higher in deep groundwater and 24 times higher in island groundwater. The δ¹³C_DIC indicate that DIC production in groundwater is from organic matter oxidation and in island groundwater from organic matter oxidation and dissolution of sodium carbonate salts. The ionic and isotopic evolution of the groundwater relative to evaporated river water indicates two independent pools of DIC.     

Investigating landfill‐impacted groundwater seepage into headwater streams using stable carbon isotopes

The impact of landfill contaminated groundwater along a reach of a small stream adjacent to a municipal landfill was investigated using stable carbon isotopes as a tracer. Groundwater below the stream channel, groundwater seeping into the stream, groundwater from the stream banks and stream water were sampled and analysed for dissolved inorganic carbon (DIC) and the isotope ratio of DIC (δ¹³C_DIC). Representative samples of groundwater seeping into the stream were collected using a device (a ‘seepage well’) specifically designed for collecting samples of groundwater seeping into shallow streams with soft sediments. The DIC and δ¹³C_DIC of water samples ranged from 52 to 205 mg C/L and ?16·9 to +5·7‰ relative to VPDB standard, respectively. Groundwater from the stream bank adjacent to the landfill and some samples of groundwater below the stream channel and seepage into the stream showed evidence of δ¹³C enriched DIC (δ¹³C_DIC = ?2·3 to +5·7‰), which we attribute to landfill impact. Stream water and groundwater from the stream bank opposite the landfill did not show evidence of landfill carbon (δ¹³C_DIC = ?10·0 to ?16·9‰). A simple mixing model using DIC and δ¹³C_DIC showed that groundwater below the stream and groundwater seeping into the stream could be described as a mixture of groundwater with a landfill carbon signature and uncontaminated groundwater. This study suggests that the hyporheic zone at the stream–groundwater interface probably was impacted by landfill contaminated groundwater and may have significant ecological implications for this ecotone. Copyright © 2004 John Wiley & Sons, Ltd.     

Characteristics of δ13CDIC in lakes on the Tibetan Plateau and its implications for the carbon cycle

Dissolved inorganic carbon isotope (δ¹³C_DIC) is an important tool to reveal the carbon cycle in lake systems. However, there are only few studies focusing on the spatial variation of δ¹³C_DIC of closed lakes. Here we analyze the characteristics of δ¹³C_DIC of 24 sampled lakes (mainly closed lakes) across the Qiangtang Plateau (QTP) and identify the driving factors for its spatial variation. The δ¹³C_DIC value of these observed lakes varies in the range of ? 15·0 to 3·2‰, with an average value of ? 1·2‰. The δ¹³C_DIC value of closed lakes is close to the atmospheric isotopic equilibrium value, much higher than that in rivers and freshwater lakes reported before. The high δ¹³C_DIC value of closed lakes is mainly attributed to the significant contribution of carbonate weathering in the catchment and the evasion of dissolved CO₂ induced by the strong evaporation of lake water. The δ¹³C_DIC value of closed lakes has a logarithmic correlation with water chemistry (TDS, DIC and pCO₂), also suggesting that the evapo‐concentration of lake water can influence the δ¹³C_DIC value. The δ¹³C_DIC value shows two opposite logarithmic correlations with lake size depending on the δ¹³C_DIC range. This study suggests that the δ¹³C in carbonates in lacustrine sediments can be taken as an indicator of lake volume variation in closed lakes on QTP. Copyright © 2011 John Wiley & Sons, Ltd.     

Dissolved inorganic carbon evolution in neutral discharge from mine tailings piles

We measured the concentrations of dissolved inorganic carbon (DIC) and major ions and the stable carbon isotope ratios of DIC (δ¹³C_DIC) in two creeks discharging from carbonate‐rich sulphide‐containing mine tailings piles. Our aim was to assess downstream carbon evolution of the tailings discharge as it interacted with the atmosphere. The discharge had pH of 6.5–8.1 and was saturated with respect to carbonates. Over the reach of one creek, the DIC concentrations decreased by 1.1 mmol C/l and δ¹³C_DIC increased by ~4.0‰ 200 m from the seep source. The decrease in the DIC concentrations was concomitant with decreases in the partial pressure of CO_2(aq) because of the loss of excess CO_2(aq) from the discharge. The corresponding enrichment in the δ¹³C_DIC is because of kinetic isotope fractionation accompanying the loss of CO_2(g). Over the reach of the other creek, there was no significant decrease in the DIC concentrations or notable changes in the δ¹³C_DIC. The insignificant change in the DIC concentrations and the δ¹³C_DIC is because the first water sample was collected 160 m away from the discharge seep, not accessible during this research. In this case, most of the excess CO_2(aq) was lost before our first sampling station. Our results indicate that neutral discharges from tailings piles quickly lose excess CO_2(aq) to the atmosphere and the DIC becomes enrich in ¹³C. We suggest that a significant amount of carbon cycling in neutral discharges from tailings piles occur close to the locations where the discharge seeps to the surface. Copyright © 2015 John Wiley & Sons, Ltd.     

Leaky savannas: the significance of lateral carbon fluxes in the seasonal tropics

Globally, dissolved inorganic carbon (DIC) accounts for more than half the annual flux of carbon exported from terrestrial ecosystems via rivers. Here, we assess the relative influences of biogeochemical and hydrological processes on DIC fluxes exported from a tropical river catchment characterized by distinct land cover, climate and geology transition from the wet tropical mountains to the low‐lying savanna plains. Processes controlling changes in river DIC were investigated using dissolved organic carbon, particulate organic carbon and DIC concentrations and stable isotope ratios of DIC (δ¹³C_DIC) at two time scales: seasonal and diel. The recently developed Isotopic Continuous Dissolved Inorganic Carbon Analyser was used to measure diel DIC concentration and δ¹³C_DIC changes at a 15‐min temporal resolution. Results highlight the predominance of biologically mediated processes (photosynthesis and respiration) controlling diel changes in DIC. These resulted in DIC concentrations varying between 3.55 and 3.82 mg/l and δ¹³C_DIC values ranging from ?19.7 ± 0.31‰ to ?17.1 ± 0.08‰. In contrast, at the seasonal scale, we observed wet season DIC variations predominantly from mixing processes and dry season DIC variations due to both mixing processes and biological processes. The observed wet season increases in DIC concentrations (by 6.81 mg/l) and δ¹³C_DIC values of river water (by 5.4‰) largely result from proportional increases in subsurface inflows from the savanna plains (C₄ vegetation) region relative to inflows from the rainforest (C₃ vegetation) highlands. The high DIC river load during the wet season resulted in the transfer of 97% of the annual river carbon load. Therefore, in this gaining river, there are significant seasonal variations in both the hydrological and carbon cycles, and there is evidence of substantial coupling between the carbon cycles of the terrestrial and the fluvial environments. Recent identification of a substantial carbon sink in the savannas of northern Australia during wetter years in the recent past does not take into account the possibility of a substantial, rapid, lateral flux of carbon to rivers and back to the atmosphere. Copyright © 2015 John Wiley & Sons, Ltd.     

A multi‐tracer approach to quantifying groundwater inflows to an upland river; assessing the influence of variable groundwater chemistry

Understanding the behaviour and variability of environmental tracers is important for their use in estimating groundwater discharge to rivers. This study utilizes a multi‐tracer approach to quantify groundwater discharge into a 27 km upland reach of the Gellibrand River in southwest Victoria, Australia. Ten sampling campaigns were conducted between March 2011 and June 2012, and the distribution of ²²²Rn activities, Cl and ³H concentrations imply the river receives substantial groundwater inflows. Mass balances based on ²²²Rn, Cl and ³H yield estimates of groundwater inflows that agree to within ± 12%, with cumulative inflows in individual campaigns ranging from 24 346 to 88 467 m³/day along the studied river section. Groundwater discharge accounts for between 10 and 50% of river flow dependent on the time of year, with a high proportion (>40 %) of groundwater sustaining summer flows. Groundwater inflow is largely governed by regional groundwater flowpaths; between 50 and 90% of total groundwater inflows occur along a narrow 5–10 km section where the river intersects the Eastern View Formation, a major regional aquifer. Groundwater ²²²Rn activities over the 16 month period were spatially heterogeneous across the catchment, ranging between 2000 Bq/m³ and 16 175 Bq/m³. Although groundwater ²²²Rn activities display temporal variation, spatial variation in groundwater ²²²Rn is a key control on ²²²Rn mass balances in river catchments where groundwater and river ²²²Rn activities are within an order of magnitude of each other. Calculated groundwater discharges vary from 8.4 to 15 m³/m/day when groundwater ²²²Rn activities are varied by ± 1 σ. Copyright © 2013 John Wiley & Sons, Ltd.     

Dissolved inorganic carbon isotopes of a typical alpine river on the Tibetan Plateau revealing carbon sources,wetland effect and river recharge

The Nyangqu River, the largest right bank tributary of the Yarlung Zangbo River in the Qinghai–Tibet Plateau, was representative of an alpine riverine carbon cycle experiencing climate change. In this study, dissolved inorganic carbon (DIC) spatial and seasonal variations, as well as their carbon isotopic compositions (δ¹³C_DIC) in river water and groundwater were systematically investigated to provide constraints on DIC sources, recharge and cycling. Significant changes in the δ¹³C_DIC values (from −2.9‰ to −23.4‰) of the water samples were considered to be the result of different contributions of two dominant DIC origins: soil CO₂ dissolution and carbonate weathering. Three types of rock weathering (dissolution of carbonate minerals by H₂CO₃ and H₂SO₄, and silicate dissolution by H₂CO₃) were found to control the DIC input into the riverine system. In DIC cycling, groundwater played a significant role in delivering DIC to the surface water, and DIC supply from tributaries to the main stream increased from the dry season to the wet season. Notably, the depleted δ¹³C_DIC ‘peak’ around the 88.9° longitude, especially in the September groundwater samples, indicated the presence of ‘special’ DIC, which was attributed to the oxidation of methane from the Jiangsa wetland located nearby. This wetland could provide large amounts of soil organic matter available for bacterial degradation, producing ¹³C-depleted methane. Our study provided insights regarding the role of wetlands in riverine carbon cycles and highlighted the contribution of groundwater to alpine riverine DIC cycles.     

Explicit Modeling of Radon-222 in HydroGeoSphere During Steady State and Dynamic Transient Storage

Transient storage zones (TSZs) are located at the interface of rivers and their abutting aquifers and play an important role in hydrological and biogeochemical functioning of rivers. The natural radioactive tracer ²²²Rn is a particularly well-suited tracer for studying TSZ water exchange and age. Although ²²²Rn measurement techniques have developed rapidly, there has been less progress in modeling ²²²Rn activities. Here, we combine field measurements with the numerical model HydroGeoSphere (HGS) to simulate ²²²Rn emanation, decay and transport during steady state (riffle-pool sequence) and transient (bank storage) conditions. Comparing the HGS mean water ages with the conventional ²²²Rn apparent ages during steady state showed a systemic underestimation of apparent age with increasing dispersion and especially where large concentration gradients exist within the subsurface. A large underestimation of apparent water age was also observed at the advective front during bank storage where regional high ²²²Rn groundwater mixes with newly infiltrated surface water. The explicit modeling of radiogenic tracers such as ²²²Rn offers a physical interpretation of this data as well as a useful way to test simplified apparent age models.     

Tracking Groundwater Discharge to a Large River using Tracers and Geophysics

Few studies have investigated large reaches of rivers in which multiple sources of groundwater are responsible for maintaining baseflow. This paper builds upon previous work undertaken along the Fitzroy River, one of the largest perennial river systems in north‐western Australia. Synoptic regional‐scale sampling of both river water and groundwater for a suite of environmental tracers (⁴He, ⁸⁷Sr/⁸⁶Sr, ²²²Rn and major ions), and subsequent modeling of tracer behavior in the river, has enabled definition and quantification of groundwater input from at least three different sources. We show unambiguous evidence of both shallow “local” groundwater, possibly recharged to alluvial aquifers beneath the adjacent floodplain during recent high‐flow events, and old “regional” groundwater introduced via artesian flow from deep confined aquifers. We also invoke hyporheic exchange and either bank return flow or parafluvial flow to account for background ²²²Rn activities and anomalous chloride trends along river reaches where there is no evidence of the local or regional groundwater inputs. Vertical conductivity sections acquired through an airborne electromagnetic (AEM) survey provide insights to the architecture of the aquifers associated with these sources and general groundwater quality characteristics. These data indicate fresh groundwater from about 300 m below ground preferentially discharging to the river, at locations consistent with those inferred from tracer data. The results demonstrate how sampling rivers for multiple environmental tracers of different types—including stable and radioactive isotopes, dissolved gases and major ions—can significantly improve conceptualization of groundwater—surface water interaction processes, particularly when coupled with geophysical techniques in complex hydrogeological settings.     

Groundwater–surface water connectivity in a chain-of-ponds semiarid river

Semiarid rivers are often characterized by chains of small pools connected by riffles and wet meadows. The pools can be maintained by wet season surface runoff, groundwater discharge, or some combination thereof. Using synoptic surveys for several environmental tracers (δD and δ¹⁸O of H₂O, specific electrical conductance at 25°C [EC], chloride and ²²²Rn), we evaluated the groundwater—surface water connectivity of the Light River (South Australia) along an 8 km section in the vicinity of a proposed mining development. In all three surveys (representing spring, summer and winter conditions), the pools were maintained by regional groundwater discharge based on an elevated surface water EC (9–12 dS m⁻¹) similar to regional groundwater, elevated radon-222 activities (0.09–3.0 Bq L⁻¹) and low rainfall. Most pools were perennial, either because they directly received groundwater discharge or, indirectly, had an inflow originating from upstream groundwater-fed pools. The elevated salinity of regional groundwater is a key factor for the maintenance of perennial pools in the Light River because the potential for baseflow depletion by groundwater pumping is more limited.     

Riverine groundwater discharge estimation in a dynamic river corridor using 222Rn

Groundwater discharge flux into rivers (riverine groundwater discharge or RGD) is essential information for the conservation and management of aquatic ecosystems and resources. One way to estimate area-integrated groundwater discharge into surface water bodies is to measure the concentration of a groundwater tracer within the water body. We assessed groundwater discharge using ²²²Rn, a tracer common in many surface water studies, through field measurements, surface water ²²²Rn mass balance model, and groundwater flow simulation, for the seldom studied but ubiquitous setting of a flooding river corridor. The investigation was conducted at the dam-regulated Lower Colorado River (LCR) in Austin, Texas, USA. We found that ²²²Rn in both the river water and groundwater in the river bank changed synchronously over a 12-hour flood cycle. A ²²²Rn mass balance model allowed for estimation of groundwater discharge into a 500-m long reach of the LCR over the flood. The groundwater discharge ranged between negative values (indicating recharge) to 1570 m³/h; groundwater discharge from groundwater flow simulations corroborated these estimates. However, for the dynamic groundwater discharge estimated by the ²²²Rn box model, assuming whether the groundwater ²²²Rn endmember was constant or dynamic led to notably different results. The resultant groundwater discharge estimates are also highly sensitive to river ²²²Rn values. We thus recommend that when using this approach to accurately characterize dynamic groundwater discharge, the ²²²Rn in near-stream groundwater should be monitored at the same frequency as river ²²²Rn. If this is not possible, the ²²²Rn method can still provide reasonable but approximate groundwater discharge given background information on surface water-groundwater exchange time scales.     

Spatiotemporal variations of dissolved inorganic carbon and controlling factors in a small karstic catchment,Southwestern China

Dissolved inorganic carbon (DIC) is the most important carbon component in karst aquatic system where fluid is highly transmissive, but has rarely been examined in the subtropical karst critical zone (K-CZ). In this study, concentrations of dissolved solutes and isotopic compositions of DIC (δ¹³C_DIC) at 11 sites of a 73.4 km² karstic catchment in Southwestern China were analysed monthly in order to uncover the spatiotemporal variations of both DIC and its dominant sources, and to identify relevant controlling factors. Both DIC concentrations and δ¹³C_DIC were highly variable, ranging from 2.52 to 5.85 mmol l⁻¹ and from −15.7 to −4.5‰, respectively. DIC in underground water (UGW) was higher in concentration and more depleted in ¹³C compared to surface water (SFS). DIC concentrations showed an inconsistent seasonal trend with other solutes, with higher values in the wet season at some sites. δ¹³C_DIC values were lower in the wet season than in the dry season. The results of mixing model IsoSource revealed spatiotemporal patterns of DIC sources. During the dry season, carbonate weathering was the primary contributor to DIC in UGW (excluding in the middle reaches). However, during the wet season, soil CO₂ was the dominant source of DIC in both UGW and SFS, and it was higher than in the dry season. Overall, there are significant spatiotemporal disparities and highly transmissive characteristics of both DIC and its sources in the K-CZ, which are controlled by multiple factors. This study also highlights that rainfall may play a crucial role in accelerating carbon dynamics in the K-CZ. High-frequency sampling campaigns in high-flow periods and deep analyses are needed in future work to elucidate the related processes and mechanisms. © 2019 John Wiley & Sons, Ltd.     

Contrasting carbon export dynamics of human impacted and pristine tropical catchments in response to a short‐lived discharge event

Utilising newly available instrumentation, the carbon balance in two small tropical catchments was measured during two discharge events at high temporal resolution. Catchments share similar climatic conditions, but differ in land use with one draining a pristine rainforest catchment, the other a fully cleared and cultivated catchment. The necessity of high resolution sampling in small catchments was illustrated in each catchment, where significant chemical changes occurred in the space of a few hours or less. Dissolved and particulate carbon transport dominated carbon export from the rainforest catchment during high flow, but was surpassed by degassing of CO₂ less than 4 h after the discharge peak. In contrast, particulate organic carbon dominated export from the cleared catchment, in all flow conditions with CO₂ evasion accounting for 5–23% of total carbon flux. Stable isotopes of dissolved inorganic carbon (DIC) in the ephemeral rainforest catchment decreased quickly from ~1.5 ‰ to ~ ?16 ‰ in 5 h from the flood beginning. A two‐point mixing model revealed that in the initial pulse, over 90% of the DIC was of rainwater origin, decreasing to below 30% in low flow. In the cultivated catchment, δ¹³C_DIC values varied significantly less (?11.0 to ?12.2 ‰) but revealed a complex interaction between surface runoff and groundwater sources, with groundwater DIC becoming proportionally more important in high flow, due to activation of macropores downstream. This work adds to an increasing body of work that recognises the importance of rapid, short‐lived hydrological events in low‐order catchments to global carbon dynamics. Copyright © 2013 John Wiley & Sons, Ltd.     

Factors controlling carbon isotope ratios of dissolved inorganic carbon in two major tributaries of the Han River,Korea

Understanding the carbon cycle of the Han River system in Korea is of prime interest in managing and preserving this valuable water resource for more than 20 million residents in the area. As a part of a comprehensive carbon cycling study for the Han River system, this report focuses on the carbon isotope compositions of dissolved inorganic carbon (DIC) in its two major tributaries, the North and the South Han Rivers. The major difference in carbonate chemistry of the tributaries originates primarily from the lithology of the catchment areas. The South Han River, draining a carbonate‐dominant terrain, has much higher alkalinities and DIC concentrations, whereas the lower concentrations in the North Han River indicate little influence of carbonate weathering. Likewise, δ¹³C_DIC values in the South Han River indicate that the DIC input from the carbonate rocks is important in controlling carbon isotope ratios of DIC. For the North Han River, the oxidation of organic material influences the amount of riverine DIC and δ¹³C_DIC values to a greater extent. Overall, remarkable seasonal and spatial variations of river chemistry and carbon isotope compositions of DIC reflect the variability in geo‐hydrologic characteristics, in the water regime, and in metabolic activities in the river water and/or the drainage areas. Copyright © 2006 John Wiley & Sons, Ltd.     

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.     

Sub‐surface water contribution to recession flow in a mountain headwater stream system based on single monitoring campaign

Discharge in mountain streams may be a mixture of snowmelt, water from surface runoff, and deep return flow through valley bottom alluvia. We used δ¹⁸O and δ²H, solute concentrations, and ²²²Rn to determine water sources of a headwater stream located at the McDonald Creek watershed, Glacier National Park, USA, during summer recession flow period. We analysed minimal water isotope ranges of ?17.6‰ to ?16.5‰ and ?133‰ to ?121‰ for δ¹⁸O and δ²H, respectively, potentially due to dominance of snow‐derived water in the stream. Likewise, solute concentrations measured in the stream through the watershed showed minimal variation with little indication of subsurface water input into the stream. However, we observed ²²²Rn activities in the stream that ranged from 39 to 2646 Bq/m³ with the highest value measured in middle of the watershed associated with channel constriction corresponding to changes in local orientation of underlying rocks. Downstream from this point, ²²²Rn activity decreased from 581 to 117 Bq/m³ in a series of punctuated steps associated with small rapids and waterfalls that we hypothesized to cause radon degassing with a maximum predicted loss of 427 Bq/m³ along a 400 m distance. Based on mass balance calculations using ²²²Rn activity values, streamflow, and channel characteristics, we estimated that groundwater contributed between 0.3% and 29% of total flow. Overall, we estimated a 5.9% of groundwater contribution integrated for stream reach measured at McDonald Creek during recession flow period. Finally, a lower mean hyporheic flux of 14 m³/day was estimated compared to the groundwater flux of 70 710 m³/day. These assessments highlight the potential for radon as a conservative tracer that can be used to estimate subsurface water contribution in mountain streams within a complex geologic setting. Copyright © 2015 John Wiley & Sons, Ltd.     

Carbon isotopes in the rivers from the Lesser Antilles: origin of the carbonic acid consumed by weathering reactions in the Lesser Antilles

In this paper, we use carbon isotopes in the dissolved load of rivers from the Lesser Antilles volcanic arc (Guadeloupe, Martinique and Dominica islands) to constrain the source of the carbon dioxide (CO₂) involved in the neutralization reactions during water–rock interactions. The δ¹³C data span a large range of variations, from –19‰ to –5 · 2‰ for DIC (dissolved inorganic carbon) concentrations ranging from 11 μM to 2000 μM. Coupled with major element concentrations, carbon isotopic ratios are interpreted as reflecting a mixture of magmatic CO₂ (enriched in heavy carbon (δ¹³C ≈ –3 · 5‰) and biogenic CO₂ produced in soils (enriched in light carbon (δ¹³C < –17‰)). Carbon isotopes show that, at the regional scale, 23 to 40% of CO₂ consumed by weathering reactions is of magmatic origin and is transferred to the river system through aquifers under various thermal regimes. These numbers remain first‐order estimates as the major uncertainty in using carbon isotopes as a source tracer is that carbon isotopes can be fractionated by a number of processes, including soil and river degassing. Chemical weathering is clearly, at least, partly controlled by the input of magmatic CO₂, either under hydrothermal (hot) or surficial (cold) weathering regimes. This study shows that the contribution of magmatic CO₂ to chemical weathering is an additional parameter that could explain the high weathering rates of volcanic rocks. The study also shows that a significant part of the carbon degassed from the Earth's interior is not released as CO₂ to the atmosphere, but as DIC to the ocean because it interacts with the groundwater system. This study calls for a better understanding of the contributions of deep carbon to the hydrosphere and its influence on the development of the Critical Zone. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

Using environmental isotopes to investigate the groundwater recharge mechanisms and dynamics in the North-eastern Basin,Palestine

ABSTRACT

This study aims to differentiate the potential recharge areas and flow mechanisms in the North-eastern Basin, Palestine. The results differentiate the recharge into three main groups. The first is related to springs and some of the deep wells close to the Anabta Anticline, through the Upper Aquifer (Turonian) formation, with depleted δ¹⁸O and δ²H. The second is through the Upper Cenomanian formation surrounding the Rujeib Monocline in the southeast, where the lineament of the Faria Fault plays an important role, with relatively enriched δ¹³C_DIC values of about ?4‰ (VPDB). The third is the Jenin Sub-series, which shows higher δ¹³C_DIC values, with enriched δ¹⁸O and δ²H and more saline content. The deep wells from the Nablus area in the south of the basin indicate low δ¹³C_DIC values due to their proximity to freshwater infiltrating faults. The deep wells located to the northwest of the basin have δ¹³C_DIC values from ?8 to ?9‰ (VPDB), with enriched δ¹⁸O signatures, indicating slow recharge through thick soil.     

Determination of groundwater discharge rates and water residence time of groundwater‐fed lakes by stable isotopes of water (18O, 2H) and radon (222Rn) mass balances

Lacustrine groundwater discharge (LGD) and the related water residence time are crucial parameters for quantifying lake matter budgets and assessing its vulnerability to contaminant input. Our approach utilizes the stable isotopes of water (δ¹⁸O, δ²H) and the radioisotope radon (²²²Rn) for determining long‐term average and short‐term snapshots in LGD. We conducted isotope balances for the 0.5‐km² Lake Ammelshainer See (Germany) based on measurements of lake isotope inventories and groundwater composition accompanied by good quality and comprehensive long‐term meteorological and isotopic data (precipitation) from nearby monitoring stations. The results from the steady‐state annual isotope balances that rely on only two sampling campaigns are consistent for both δ¹⁸O and δ²H and suggested an overall long‐term average LGD rate that was used to infer the water residence time of the lake. These findings were supported by the good agreement of the simulated LGD‐driven annual cycles of δ¹⁸O and δ²H lake inventories with the observed lake isotope inventories. However, radon mass balances revealed lower values that might be the result of seasonal LGD variability. For obtaining further insights into possible seasonal variability of groundwater–lake interaction, stable water isotope and radon mass balances could be conducted more frequently (e.g., monthly) in order to use the derived groundwater discharge rates as input for time‐variant isotope balances.