Stable isotope analysis of carbon cycling in the Perdido estuary, Florida

Stable carbon isotope (δ¹³C) analysis was used in the Peridido Estuary, Florida U.S. to determine the predominant carbon source that supports the bacterial assemblage. Stable carbon isotope values were measured in the suspended particulate matter (SPM), dissolved organic and inorganic matter, and bacteria. Stable nitrogen isotope (δ¹⁵N) ratios were measured in SPM and nitrate to assist in understanding carbon cycling through the estuary. Analyses were conducted on samples from riverine, coastal, and anthropogenic sources and compared with samples from the bay. Stable isotope ratio analysis was coupled with estimates of mixing of riverine and coastal waters into the bay. Preliminary observation of the °¹³C data indicates that terrestrial organic matter is the primary carbon source that is assimilated by bacteria in the ecosystem. Stable isotope data from carbon and nitrogen pools in combination with analysis of estuarine current velocities indicates that primary production is an important factor in the carbon cycle. This study demonstrates the importance of stable isotope analysis of multiple carbon and nitrogen pols to assess sources and cycling of organic matter.     

Using Stable Isotope Mixing in a Great Lakes Coastal Tributary to Determine Food Web Linkages in Young Fishes

We characterized stable isotope mixing along a river-Great Lake transition zone in the St. Louis River, an important fish nursery in western Lake Superior, and used it to identify food web linkages supporting young fish production. We observed a broad, spatial pattern in the carbon stable isotope ratio (δ¹³C); downriver enrichment in particulate organic carbon and aquatic vegetation δ¹³C, as well as pelagic, benthic and littoral invertebrate δ¹³C, reflected isotope mixing along the river-lake transition zone. Fishes with similarly enriched δ¹³C were used to identify benthopelagic and littoral trophic pathways. River and Lake Superior organic matter (OM) sources contributed to both pathways. Differences between the δ¹³C in fishes and invertebrate prey revealed that fish production was supported at multiple spatial scales. The result was that the food web specific to any location along the transition zone incorporated multiple OM sources from across the watershed.     

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.     

Stable isotope analyses (δ<Superscript>15</Superscript>N and δ<Superscript>13</Superscript>C) of the trophic relationships of<Emphasis Type="Italic">Callinectes sapidus</Emphasis> in two North Carolina estuaries

The present study focused on detecting variations in trophic relationships among blue crab (Callinectes sapidus) consumers according to water quality along two estuaries in North Carolina. Stable isotope (δ¹⁵N and δ¹³C) analyses of particulate organic matter and bivalve(Rangia cuneata andCorbicula fluminea) food sources were examined in combination with an Isosource mixing model. Results suggest that blue crab δ¹³C values increased significantly with increasing salinity from upper to lower sites along the Neuse River estuary (NRE; R2 = 0.87, p < 0.01) and Alligator River estuary (R² = 0.92, p < 0.01). There was a positive relationship between blue crab δ¹⁵N values and nitrate concentrations for the NRE (R² = 0.48, p = 0.12). This study found that blue crab δ¹³C values increased with salinity from upper to lower regions along both estuaries. Results suggest that blue crab production may have used alternative food sources that were isotopically (δ¹³C) depleted, especially in the upper NRE, and enriched sources in the mid to lower regions of both estuaries. Consumers sampled from the upper NRE may be influenced by higher nitrogen input from urban land use and municipal wastewater.     

Limitations in the use of compound-specific stable isotope analysis to understand the behaviour of a complex BTEX groundwater contamination near Brussels (Belgium)

The application of compound-specific stable isotope analysis (CSIA) was evaluated to characterise a complex groundwater contamination. For this purpose, δ¹³C and δ²H analysis of benzenes and alkylated derivatives were used to interpret both the impact of different sources on a contaminant plume and the presence of degradation processes. The different contaminant sources could be distinguished based on their combined δ¹³C–δ²H signature of the benzene, toluene, ethylbenzene and xylenes (BTEX) dissolved in the groundwater. Despite this source differentiation, plume characterisation was not possible due to the complex mixing of the respective contaminant plumes. Furthermore, the original isotope signatures of the sources were not preserved across these plumes. To estimate the level of in situ biodegradation independently from concentration data, the Rayleigh equation was used. Although current literature identifies the application of CSIA as very promising in the frame of characterising organic groundwater pollution, this study has indicated that this approach can be limited with respect to successfully distinguish the different plumes and their relation to the known source zones.     

Plankton and dissolved inorganic carbon isotopic composition in a river-dominated estuary: Apalachicola Bay, Florida

To characterize the isotopic composition of organisms at the base of the food web and the controls on their variability, the concentration and δ¹³C isotopic composition of dissolved inorganic carbon (DIC) and plankton δ¹³C, δ¹⁵N, and δ³⁴S were measured. The measurements were made during periods of high and low river flow in Apalachicola Bay, Florida, United States, over 3 yr. DIC concentration and δ¹³C values were related to salinity, indicating that conservative mixing of riverine and marine waters was responsible for the overall distributions. The usefulness of DIC δ^13C data for characterizing the trophic processes within the estuary was dependent upon the residence time of water within the season. Plankton δ¹³C values varied from −22‰ to −30‰ and were directly related to estuarine DIC δ¹³C, offset by a factor of roughly −20‰. This offset factor varied with salinity. Values of δ³⁴S in estuarine plankton (station means ranged from 11.4‰ to 13.1‰) were depleted relative to marine plankton (17.7±0.4‰) possibly due to the admixture of³⁴S-depleted sedimentary sulfide with estuarine samples. Values of δ³⁴S in plankton were not related to δ¹³C values of plankton and were only weakly correlated to the salinity of the water from which the plankton were collected, indicating that marine sulfate was the primary source of planktonic sulfur. Values of δ¹⁵N in plankton varied from 5.5‰ to 10.7‰ and appeared related to dominance of the sample by phytoplankton or zooplankton. Estuarine plankton was¹⁵N enriched relative to offshore plankton and estuarine sediment.     

Metabolic effects on stable carbon isotopic composition of freshwater bivalve shell Corbicula fluminea

The stable isotopic composition of the bivalve shell has been widely used to reconstruct the pa-laeo-climate and palaeo-environment. The climatic and environmental significance of carbon isotopic composition of the bivalve shell is still in dispute, and incorporation of metabolic carbon can obscure carbon isotope records of dis-solved inorganic carbon. This study deals with freshwater bivalve, Corbicula fluminea aragonite shell. The results indicated that the δ13C values of bivalve shells deposited out of equilibrium with the host water and showed an onto-genic decrease, indicating that there are metabolic effects and more metabolic carbon is incorporated into larger shells. The proportion of metabolic carbon of shells varies between 19.8% and 26.8%. However, δ13CS can still be used as qualitative indicators of δ13CDIC and environmental processes that occurred during shell growth.     

Trophic Relationships of a Marsh Bird Differ Between Gulf Coast Estuaries

Much of North America’s tidal marsh habitat has been significantly altered by both natural and man-made processes. Thus, there is a need to understand the trophic ecology of organisms endemic to these ecosystems. We applied carbon (δ ¹³C) and nitrogen (δ ¹⁵N) stable isotope analysis, along with isotope mixing models, to egg yolk, liver, and muscle tissues of clapper rails (Rallus longirostris) and their likely prey items. This analysis enabled us to explore variation in trophic niche and diet composition in this important marsh bird in two northern Gulf of Mexico tidal marshes that are river and ocean-dominated. For the river-associated estuary, δ ¹³C and δ ¹⁵N of egg yolks, liver, and pectoral muscle tissue samples provided evidence that clapper rails maintained a similar diet during both the winter and the breeding season. A trophic link between C₃ primary productivity and the clapper rail’s diet was also indicated as the δ ¹³C of clapper rail egg yolks related negatively with the aerial cover of C₃ macrophytes. Clapper rails from the ocean-dominated estuary had a narrower trophic niche and appeared to be utilizing marine resources, particularly, based on modeling of liver stable isotope values. Variation in stable isotope values between egg yolk and liver/muscle in both systems suggests that endogenous resources are important for egg production in clapper rails. These results demonstrate that diet composition, prey source, and niche width of clapper rails can vary significantly across different estuaries and appear to be influenced by hydrological conditions.     

Interaction between deep and shallow groundwater systems in areas affected by Quaternary tectonics (Central Italy): a geochemical and isotope approach

Hydro- and isotope geochemistry are used to refine groundwater conceptual models in two areas of central Italy (Acque Albule Basin and Velino River Valley) affected by extensional Quaternary tectonics, where deep and shallow groundwater flow systems are interacting. The role of geology, of recent deposits filling the plains and of main tectonic features controlling groundwater flowpaths and deep-seated fluids emergences are investigated and discussed. Environmental isotopes (²H and ¹⁸O) confirm recharge in the surrounding carbonate aquifers, and meteoric origin of both shallow and deep groundwater. Major ion chemistry indicates a mixing between shallow Ca-HCO₃ groundwater from carbonate aquifers and deep Ca-HCO₃-SO₄ groundwater, characterised by higher salinity and temperature and high concentration in sulphates. Isotopic composition of dissolved sulphates (δ ³⁴S and δ ¹⁸O) and dissolved inorganic carbon (δ ¹³C), henceforth indicated as DIC, are used to verify the presence of different sources of groundwater, and to validate the mixing model suggested by the major ion analyses. Sulphate isotope composition suggests a marine origin for the groundwater characterised by elevated sulphate concentration, whose source is present in the deep buried sequences. Carbon isotope composition confirms the role of a DIC source associated to CO₂ degassing of a deep reservoir. Groundwater conceptual models are improved underlining the importance of Plio-Pleistocene sequences filling the tectonic depression. In the Acque Albule area, the travertine plateau represents a mixing stratified aquifer, where deep groundwater contribution is spread into the shallow aquifer. The alluvial–clastic–lacustrine leaky aquifer of Velino Valley enables a complete mixing of shallow and deep groundwater allowing spot-located discharge of deep groundwater along tectonic patterns and facilitating sulphate reduction in the lacustrine sediments, explaining locally the presence of H₂S.     

Determination of Trophic Transfer at a Created Intertidal Oyster (<Emphasis Type="Italic">Crassostrea ariakensis</Emphasis>) Reef in the Yangtze River Estuary Using Stable Isotope Analyses

Oysters can create reefs that provide habitat for associated species resulting in elevated resident abundances, lower mortality rates, and increased growth and survivorship compared to other estuarine habitats. However, there is a need to quantify trophic relationships and transfer at created oyster reefs to provide a better understanding of their potential in creating suitable nekton habitat. Stable isotope analyses (δ¹³C and δ¹⁵N) were conducted to examine the organic matter sources and potential energy flow pathways at a created intertidal oyster (Crassostrea ariakensis; hereinafter, oyster) reef and adjacent salt marsh in the Yangtze River estuary, China. The δ¹³C values of most reef-associated species (22 of 37) were intermediate between those of suspended particle organic matter (POM) and benthic microalgae (BMI), indicating that both POM and BMI are the major organic matter sources at the created oyster reef. The sessile and motile macrofauna colonizing the reef make up the main prey of transient nekton (e.g., spotted sea bass, Asian paddle crab, and green mud crab), thus suggesting that the associated community was most important in supporting higher trophic levels as opposed to the direct dietary subsidy of oysters. The created oyster reef consistently supported higher trophic levels than the adjacent salt marsh habitat due to the dominance of secondary consumers. These results indicate that through the provision of habitat for associated species, created oyster reefs provide suitable habitat and support a higher average trophic level than adjacent salt marsh in the Yangtze River estuary.     

Eutrophication processes and trophic interactions in a shallow estuary: Preliminary results based on stable isotope analysis (δ13C and δ15N)

Stable isotopes ratios (δ¹³C and δ¹⁵N) were measured in primary producers and consumers of two bays with contrasting eutrophic conditions in the Patos Lagoon estuary, southern Brazil: the Justino bay, a more pristine ecosystem, and the Mangueira bay, a heavily polluted region that receives the Rio Grande city sewage and effluencts of several industries. δ¹³C values of organisms collected in both subsystems were not different, but δ¹⁵N values had significant statistical differences, ca. 3.5‰ higher in the Mangueira bay. It is likely that primary producers and consumers in this subsystem are greatly influenced by higher nitrogen input due to domestic and industrial sewages. The stable isotope analysis also corroborated several trophic interactions previously established by gut content analysis, and due to its higher sensitivity, it was possible to better determine the contributions of different primary producers and detrital fractions to the consumers' diets. It was confirmed that plant detritus represents the main food source for most organisms. The stable isotope analysis also demonstrated that detritivorous benthic organisms in the same habitat have distinct diet compositions, with differential consumption of C3 and C4 plants. This technique showed that some consumers that eat detritus do not have in their stable isotopic signature any relationship with that of plants. It is likely that these consumers assimilate their carbon and nitrogen from other sources like microalgae or microorganisms that colonize decaying plants.     

Stable Carbon Isotope Biogeochemistry and Anthropogenic Impacts on Karst Ground Water, Zunyi, Southwest China

Natural and anthropogenic impacts on karst ground water, Zunyi, Southwest China, are discussed using the stable isotope composition of dissolved inorganic carbon and particulate organic carbon, together with carbon species contents and water chemistry. The waters can be mainly characterized as HCO₃–Ca type, HCO₃ · SO₄–Ca type, or HCO₃ · SO₄–Ca · Mg type, according to mass balance considerations. It is found that the average δ¹³C_DIC values of ground waters are higher in winter (low-flow season) than in summer (high-flow season). Lower contents of dissolved inorganic carbon (DIC) and lower values of δ¹³C_DIC in summer than in winter, indicate that local rain events in summer and a longer residence time of water in winter play an important role in the evolution of ground water carbon in karst flow systems; therefore, soil CO₂ makes a larger contribution to the DIC in summer than in winter. The range of δ¹³C_DIC values indicate that dissolved inorganic carbon is mainly controlled by the rate of carbonate dissolution. The concentrations of dissolved organic carbon and particulate organic carbon in most ground water samples are lower than 2.0 mg C L⁻¹ and 0.5 mg C L⁻¹, respectively, but some waters have slightly higher contents of organic carbon. The waters with high organic carbon contents are generally located in the urban area where lower δ¹³C_DIC values suggest that urbanization has had an effect on the ground water biogeochemistry and might threaten the water quality.     

Using dual-isotope data to trace the origin and processes of dissolved sulphate: a case study in Calders stream (Llobregat basin,Spain)

Whereas most of the reported δ³⁴S values of dissolved sulphate are positive in the Llobregat basin, Calders stream, which is a tributary of the Llobregat River, is characterised by negative values. Stream waters, sampled monthly between 1997 and 1998, and quarterly in 1999, show an overall increase in δ³⁴S from −10‰ to 0‰, coupled with an increase in Na and Cl concentration. On the other hand, the oxygen isotopic composition of dissolved sulphate, δ¹⁸O, displayed an opposite trend with a slight decrease, from +9‰ to +6‰. Detailed sampling up stream in November 2000 indicated that, contrary to most of the surficial waters of the Llobregat basin with a δ³⁴S_SO4 mainly controlled by evaporites, in Calders stream, sulphate is derived from pyrite oxidation. The dual-isotope approach, coupled with chemical data, allowed us to identify the contribution of ³⁴S-rich sulphate effluents from anthropogenic sources, while mixing models, calculated between natural and anthropogenic sources, enabled us to estimate their contribution. Sudden increases of δ³⁴S and δ¹⁸O of dissolved sulphate in stream waters are believed to be caused by a sulphate reduction process related to oil spillage. The long-term enrichment in δ³⁴S, coupled with a decrease in δ¹⁸O_SO4, from Jan-97 to Aug-99, is interpreted as a progressive increase in the contribution of pig manure.     

Isotopic composition of dissolved boron and its geochemical behavior in a freshwater-seawater mixture at the estuary of the Changjiang （Yangtze） River

The isotopic composition of dissolved boron, in combination with the elemental concentrations of B, Cl and salinities in freshwater-seawater mixed samples taken from the estuary of the Changjiang River, the largest one in China, was investigated in detail in this study. Brackish water and seawater samples from the estuary of the Changjiang River were collected during low water season in November, 1998. Boron isotopic compositions were determined by the Cs2BO^＋2-graphite technique with a analytical uncertainty of 0.2‰ for NIST SRM 951 and an average analytical uncertainty of 0.8‰ for the samples. The isotopic compositions of boron, expressed in δ^11B, and boron concentrations in the Changjiang River at Nanjing and seawater from the open marine East Sea, China, are characterized by δ^11B values of -5.4‰ and 40.0‰, as well as 0.0272 and 4.43 mg B/L, respectively. Well-defined correlations between δ^11B values, B concentrations and Cl concentrations are interpreted in terms of binary mixing between fiver input water and East Sea seawater by a process of straightforward dilution. The offsets of δ^11B values are not related to the contents of clastic sediment and to the addition of boron. These relationships favor a conservative behavior of boron at the estuarine of the Changjiang River.     

Can the nitrogen and carbon stable isotopes of the pygmy mussel,Xenostrobus securis, indicate catchment disturbance for estuaries in northern New South Wales, Australia?

The nitrogen and carbon stable isotope ratios (δ¹⁵N and δ¹³C) of the pygmy mussel,Xenostrobus securis, were determined for three estuaries with varying levels of catchment disturbance in northern New South Wales, Australia. The lower Manning River catchment supported the highest human population densities with 3% residential development and some livestock agriculture (41%); the Wallamba River catchment was mostly livestock agriculture (56%) while the Wallingat River catchment was mostly vegetated (79%). Mussels, estuarine particulate organic matter (POM), and livestock and human-derived waste were collected in two stages during the austral summers of 2001–2002 and 2002–2003 for dual carbon-nitrogen stable isotope analysis. The disturbed Manning and Wallamba River catchment mussels were enriched in¹⁵N by an average of 3.2‰ and 1.5‰, respectively, compared to the vegetated Wallingat River mussels. Mussel δ¹³C values ranged from −24.8‰ to −30.3‰ and showed an estuarine gradient becoming enriched with distance downstream within estuaries, but were unable to distinguish patterns in catchment disturbance between estuaries. The δ¹⁵N and δ¹³C values of POM showed a similar pattern to mussels, indicating a direct link between them within each estuary. A multiple regression model of mussel δ¹⁵N using the fractions of land used for livestock agriculture and residential development within 5 km zones from river networks to a distance equivalent to a tidal ellipse from sites explained 67% of the variation in mussel δ¹⁵N with 95% of the differences lying within 1.6‰ of observed values. Increasing fractions of land used for livestock agriculture depleted mussel δ¹⁵N values estimated by the regression equation, indicating the use of cow manure as a nutrient source with a value of 2.0‰. Increasing fractions of land used for residential development enriched estimated mussel δ¹⁵N, indicating the use of human-derived waste with a value of 20.8‰. Pygmy mussels are a useful long-term bio-indicator for the effects of anthropogenic catchment disturbance and nutrient enrichment in estuaries.     

Sources of dissolved organic carbon in forest soils: evidences from the differences of organic carbon concentration and isotope composition studies

There is considerable discussion and uncertainty in the literature regarding the importance of fresh litter versus older soil organic matter as sources of soil dissolved organic carbon (DOC) in forest floor. In this study, the differences of organic carbon concentration and stable isotope composition were analyzed under different background conditions to identify the origins of DOC in forest soil. The data show that there is no significant difference in SOC content between these collected soil samples (P > 0.05), but the litter-rich surface soils have relatively higher DOC concentration than the litter-lacking (P < 0.01) ones, and the δ ¹³C values of DOC (δ ¹³C_DOC) are closer to δ ¹³C of litter than δ ¹³C values of SOC (δ ¹³C_SOC). In the litter-lacking surface soil samples, the range of δ ¹³C_DOC is between δ ¹³C_SOC and δ ¹³C of dominant plant leaves. These results suggest that DOC mainly derive from litter in the litter-rich surface soil with, and the main path of DOC sources may change with surrounding conditions. In addition, δ ¹³C_SOC and δ ¹³C_DOC become more positive, and the absolute values of Δ (δ ¹³C_DOC − δ ¹³C_SOC) decrease with depth in the soil profiles, which indicate that the percentage of DOC below 5 cm, derived from degradation of humus, may increase with soil depth.     

The distribution and stable carbon isotopic composition of dissolved organic carbon in estuaries

The distributions of dissolved organic carbon (DOC) and the natural carbon isotope ratio of DOC (DO¹³C) in estuaries reflect the predominant sources and sinks of organic matter from both allochthonous and autochthonous origins. The traditional view is that DOC in land-margin ecosystems reflects mainly the mixing of land-derived and oceanic DOC. However, this view is not consistent with the bulk of our data from a survey of DOC and DO¹³C distributions in estuaries on the East and Gulf coasts of the USA. While it is accurate that the DOC in estuaries includes material derived from land and from the ocean, the distributions of DOC and DO¹³C in several estuaries reflect additional DOC inputs from estuarine phytoplankton and tidal marshes. Even when DOC concentrations were distributed conservatively, the isotopic composition of the DOC revealed the existence of a dynamic cycle of DOC input and removal in some systems.     

Carbon and oxygen isotopic composition of car- bonate cements of different phases in terrigenous siliciclastic reservoirs and significance for their origin： A case study from sandstones of the Triassic Yanchang Formation, southwestern Ordos Basin, China

Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope （their δ^18O values range from -0.3‰- -0.1‰） and lighter oxygen isotope （their δ^18O values range from -22.1‰- -19.5‰）. Generally, they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water. This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones, preserving intragranular volume and providing the mass basis for later disso- lution caused by acidic fluid flow to produce secondary porosity. Ferriferous calcites are characterized by relatively light carbon isotope with δ^13C values ranging from -8.02‰ to -3.23‰, and lighter oxygen isotope with δ^18O values ranging from -22.9‰ to -19.7‰, which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis. As the mid-late diagenetic products, ferriferous cal- cites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir. The late ankerite is relatively heavy in carbon isotope with δ^13C values ranging from -1.92‰ to -0.84‰, and shows a wide range of variations in oxygen isotopic composition, with δ^18O values ranging from -20.5‰ to -12.6‰. They are believed to have nothing to do with decarboxylation, but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation, and the alkaline diagenetic environment at the mid-late stage would promote this process.     

Tracing sources of carbon in urban groundwater using δ<Superscript>13</Superscript>C<Subscript>TDIC</Subscript> ratios

Total dissolved inorganic carbon (TDIC) and its stable isotope ratio δ¹³C_TDIC are used to trace the evolution of the carbon system of groundwater in three UK Permo-Triassic sandstone aquifers. Samples were collected from multilevel piezometers, open boreholes and sewer sampling points in the British Midlands (Nottingham, Birmingham and Doncaster) to evaluate both local and regional variations in δ¹³C_TDIC. δ¹³C samples of matrix and pore water have also been analysed in each aquifer to further constrain the interpretations. Combining δ¹³C_TDIC ratios with measurements of TDIC and pH clearly distinguishes the principal processes underlying the geochemical evolution of groundwater in Triassic sandstone aquifers, where processes can be both natural (e.g. carbonate dissolution) and anthropogenic (sewer-derived recharge). The paper shows that δ¹³C_TDIC resolves ambiguities that arise from the interpretation of TDIC and pH measurements in isolation. Field measurements demonstrate that, under natural conditions, the carbonate system evolves similarly in each aquifer. An open-system evolution during recharge largely saturates the groundwater with carbonate depending upon its availability in the sandstone matrix. The contribution of sewer exfiltration to urban recharge is readily distinguished by lower pH and higher TDIC values without significant changes in δ¹³C_TDIC.