Browsing by Author "Bryan, E"

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    Carbon dynamics in a Late Quaternary-age coastal limestone aquifer system undergoing saltwater intrusion
    (Elsevier, 2017-12-31) Bryan, E; Meredith, KT; Baker, AA; Andersen, MS; Post, VEA
    This study investigates the inorganic and organic aspects of the carbon cycle in groundwaters throughout the freshwater lens and transition zone of a carbonate island aquifer and identifies the transformation of carbon throughout the system. We determined 14C and 13C carbon isotope values for both DIC and DOC in groundwaters, and investigated the composition of DOC throughout the aquifer. In combination with hydrochemical and 3H measurements, the chemical evolution of groundwaters was then traced from the unsaturated zone to the deeper saline zone. The data revealed three distinct water types: Fresh (F), Transition zone 1 (T1) and Transition zone 2 (T2) groundwaters. The 3H values in F and T1 samples indicate that these groundwaters are mostly modern. 14CDOC values are higher than 14CDIC values and are well correlated with 3H values. F and T1 groundwater geochemistry is dominated by carbonate mineral recrystallisation reactions that add dead carbon to the groundwater. T2 groundwaters are deeper, saline and characterised by an absence of 3H, lower 14CDOC values and a different DOC composition, namely a higher proportion of Humic Substances relative to total DOC. The T2 groundwaters are suggested to result from either the slow circulation of water within the seawater wedge, or from old remnant seawater caused by past sea level highstands. While further investigations are required to identify the origin of the T2 groundwaters, this study has identified their occurrence and shown that they did not evolve along the same pathway as fresh groundwaters. This study has also shown that a combined approach using 14C and 13C carbon isotope values for both DIC and DOC and the composition of DOC, as well as hydrochemical and 3H measurements, can provide invaluable information regarding the transformation of carbon in a groundwater system and the evolution of fresh groundwater recharge. © 2017 Elsevier B.V
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    Carbon source and sink investigations in a Late Quaternary-age coastal limestone aquifer using radiocarbon of dissolved inorganic and organic carbon
    (National Centre for Groundwater Research And Training, 2017-07-11) Bryan, E; Meredith, KT; Baker, AA; Andersen, MS; Post, VEA
    This study aims to investigate the inorganic and organic aspects of the carbon cycle in groundwaters throughout a freshwater lens and mixing zone of a carbonate island aquifer and identify the sources of carbon that dissolve in the groundwater. Groundwater samples were collected from shallow (5-20 m) groundwater wells on a carbonate island in Western Australia and analysed for inorganic ions, stable water isotopes (δ18O, δ2H), 3H, 14C and 13C carbon isotope values of DIC and DOC. The composition of groundwater DOC was investigated by Liquid Chromatography-Organic Carbon Detection (LC-OCD) analysis. The presence of 3H (0.12 to 1.35 TU) in most samples indicates that groundwaters on the island are modern, however the measured 14CDIC values (8.4 to 97.2 pmc) would suggest that the carbon in most samples is older due to carbonate dissolution and recrystallisation reactions. 14CDOC values (46.6 to 105.6 pMC) were higher than 14CDIC values and were well correlated with 3H values. Deeper, saline groundwaters were characterised by an absence of 3H, and lower 14CDOC values. The DOC composition of these groundwaters was found to be different to fresher groundwaters, with higher proportions of humic substances. The 3H free, saline waters are hypothesised to be old, remnant sea water resulting from a sea level highstand that occurred between ~4.5 and 4.3 ka ago. This study shows that a combined approach utilising both DIC and DOC tracers, as well as 3H, is required to identify the sources and evolution of carbon in groundwater, and the processes that effect the application of 14C dating to groundwaters. This is important for understanding the evolution of groundwater resources and is essential for residence time calculations.
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    The evolution of stable silicon isotopes in a coastal carbonate aquifer on Rottnest Island, Western Australia
    (Copernicus Publications, 2021-07-02) Martin, AN; Meredith, KT; Baker, AA; Norman, MD; Bryan, E
    Dissolved silicon (dSi) is a key nutrient in the oceans, but data regarding Si isotopes in coastal aquifers are not widely available. Here we investigate the Si isotopic composition of 12 fresh and 16 saline groundwater samples from Rottnest Island, Western Australia, which forms part of the world's most extensive aeolianite deposit (the Tamala Limestone formation). In total, two bedrock samples were also collected from Rottnest Island for Si isotope analysis. The δ30Si values of groundwater samples ranged from −0.4 ‰ to +3.6 ‰ with an average +1.6 ‰, and the rock samples were −0.8 ‰ and −0.1 ‰. The increase in δ30Si values in fresh groundwater is attributed to the removal of the lighter Si isotopes into secondary minerals and potentially also adsorption onto Fe (oxy)hydroxides. The positive correlations between δ30Si values and dSi concentrations (ρ = 0.59; p = 0.02) and δ30Si values and Cl, but not dSi and Cl concentrations, are consistent with vertical mixing between the younger fresh groundwater and the deeper groundwater, which have undergone a greater degree of water–rock interactions. This has produced a spatial pattern in δ30Si across the aquifer due to the local hydrogeology, resulting in a correlation between δ30Si and tritium activities when considering all groundwater types (ρ = −0.68; p = 0.0002). In the deeper aquifer, the inverse correlation between dSi and Cl concentrations (ρ = −0.79; p = 0.04) for the more saline groundwater is attributed to groundwater mixing with local seawater that is depleted in dSi (< 3.6 µM). Our results from this well-constrained island aquifer system demonstrate that stable Si isotopes usefully reflect the degree of water–aquifer interactions, which is related to groundwater residence time and local hydrogeology. Our finding that lithogenic Si dissolution occurs in the freshwater lens and the freshwater–seawater transition zone on Rottnest Island appears to supports the recent inclusion of a marine–submarine groundwater discharge term in the global dSi mass balance. Geologically young carbonate aquifers, such as Rottnest Island, may be an important source of dSi in coastal regions with low riverine input and low oceanic dSi concentrations. © Author(s) 2021. This work is distributed under the Creative Commons Attribution 4.0 License.
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    How water isotopes (18O, 2H, 3H) within an island freshwater lens respond to changes in rainfall
    (Elsevier, 2020-03-01) Bryan, E; Meredith, KT; Baker, AA; Andersen, MS; Post, VEA; Treble, PC
    Coastal aquifers provide an important source of water globally. Understanding how groundwater responds to changes in rainfall recharge is important for sustainable development. To this end, we investigate how water isotopes (18O, 2H, 3H) and chloride (Cl) concentrations within an island freshwater lens respond under varying rainfall conditions in a region experiencing climate change. Uniquely, this study presents a three year dataset of groundwater collected seasonally between May 2013 and August 2016 from ten wells. Variation in all tracers was observed. The Cl and tritium (3H) show opposing seasonal variation in some sections of the lens, with higher Cl observed in the austral summer when less rainfall occurs and evapotranspiration is highest. The opposite occurs in the austral winter months when 3H increases from atmospheric input via rainfall recharge, and Cl is diluted. An overall decline in 3H values and enrichment in stable water isotopes over the study period was also observed. This study shows that understanding groundwater of freshwater lenses should not rely on a single sampling campaign because seasonal variability is large. The identification of a dual recharge regime, with contributions from both winter rainfall and episodic events, has important implications for understanding the future fate of the freshwater lens on Rottnest Island. The finding that episodic rainfall is a major contributor to groundwater recharge is important and can only be assessed with a multi-year isotope dataset for groundwater and rainfall. © 2019 Elsevier Ltd
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    Island groundwater resources, impacts of abstraction and a drying climate: Rottnest Island, Western Australia
    (Elsevier, 2016-11) Bryan, E; Meredith, KT; Baker, AA; Post, VEA; Andersen, MS
    Coastal aquifers provide a source of water for more than one billion people, with island freshwater lenses being some of the most vulnerable coastal groundwater systems due to their susceptibility to saltwater intrusion. Basic hydrogeological and hydrochemical knowledge regarding the recharge and salinisation processes of freshwater lenses is important to ensure sustainable utilisation, especially considering possible climate change effects. This paper makes an assessment of the fate of a freshwater lens in a drying climate through a comparison of current and historic hydrochemical data, which to the author’s knowledge is unique to this study. Fresh groundwater stable isotope signatures (δ18O, δ2H) reflect local amount weighted rainfall signatures (δ18O: −3.8‰; δ2H: −15.1‰), and confirm rainfall as the origin of fresh groundwater (δ18O: −4.47 to −3.82‰; δ2H: −20.0 to −16.6‰). Mixing with seawater was identified through enriched groundwater δ18O and δ2H signatures (maximum values of −0.36‰ and −1.4‰ respectively) compared to local rainfall and higher salinity (maximum 29,267 mg/L Total Dissolved Solids (TDS)) in a number of monitoring wells around the freshwater lens. Enhanced seawater intrusion detected in the northern section of the lens area was identified through significantly increased TDS values over the last 20–40 years, with increases of up to 3000% observed between 1990 and 2014. A reduction in the extent of freshwater by approximately 1 km2 was identified since 1977, which was found to be primarily caused by a reduction in recharge to the freshwater lens due to a ∼20% decline in winter rainfall in the south-west Western Australian region since the mid 1960s. Groundwater abstraction was found to equate to between 5% and 9% of the estimated recharge for the island, and is not a significant factor in the reduction of the lens extent compared to the observed decline in rainfall recharge. Interestingly, seawater intrusion into the fresh water lens was found to occur by older seawater (0.03–0.09 TU) in regions of the lens that were previously fresh or slightly brackish, while one sample (0.67 TU) suggests either modern seawater intrusion or mixing of older saline groundwaters (>60 years) with rainfall recharge. The use of tritium dating in this island aquifer was essential in identifying ‘older’ seawater that was previously unidentified until now. The isotopic and hydrochemical tools used in this paper quantify the effects of groundwater abstraction and climate variability on the freshwater lens and have implications for the sustainable management of the groundwater resource on Rottnest Island, and elsewhere. © 2016 Elsevier B.V
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    Isotopic and chromatographic fingerprinting of the sources of dissolved organic carbon in a shallow coastal aquifer
    (European Geosciences Union, 2020-04-30) Meredith, KT; Baker, AA; Andersen, MS; O'Carroll, DM; Rutlidge, H; McDonough, LK; Oudone, PP; Bryan, E; Zainuddin, NS
    The terrestrial subsurface is the largest source of freshwater globally. The organic carbon contained within it and processes controlling its concentration remain largely unknown. The global median concentration of dissolved organic carbon (DOC) in groundwater is low compared to surface waters, suggesting significant processing in the subsurface. Yet the processes that remove this DOC in groundwater are not fully understood. The purpose of this study was to investigate the different sources and processes influencing DOC in a shallow anoxic coastal aquifer. Uniquely, this study combines liquid chromatography organic carbon detection with organic (δ13CDOC) carbon isotope geochemical analyses to fingerprint the various DOC sources that influence the concentration, carbon isotopic composition, and character with respect to distance from surface water sources, depth below surface, and inferred groundwater residence time (using 3H activities) in groundwater. It was found that the average groundwater DOC concentration was 5 times higher (5 mg L−1) than the global median concentration and that the concentration doubled with depth at our site, but the chromatographic character did not change significantly. The anoxic saturated conditions of the aquifer limited the rate of organic matter processing, leading to enhanced preservation and storage of the DOC sources from peats and palaeosols contained within the aquifer. All groundwater samples were more aromatic for their molecular weight in comparison to other lakes, rivers and surface marine samples studied. The destabilization or changes in hydrology, whether by anthropogenic or natural processes, could lead to the flux of up to 10 times more unreacted organic carbon from this coastal aquifer compared to deeper inland aquifers. © Author(s) 2020.
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    Lithium and strontium isotope dynamics in a carbonate island aquifer, Rottnest Island, Western Australia
    (Elsevier, 2020-05-01) Martin, AN; Meredith, KT; Norman, MD; Bryan, E; Baker, AA
    Water-rock interactions in aquifer systems are a key control on water quality but remain poorly understood. Lithium (Li) isotopes are useful for understanding water-rock interactions, but there are few data available for groundwater aquifers. Here we present a Li isotope dataset for rainfall and groundwater samples from a carbonate island aquifer system: Rottnest Island, Western Australia. This dataset was complemented by strontium (Sr) isotope and major and trace element data for groundwaters, and leaching experiments on bedrock samples. The δ7Li values and 87Sr/86Sr ratios of fresh groundwaters ranged from +23 to +36‰ and 0.709167 to 0.709198, respectively. Mass balance calculations indicated that silicate weathering supplied ~60 and 70% of dissolved Li and Sr in fresh groundwaters, respectively, with the remainder provided by atmospheric input, and carbonate weathering; for major cations, the majority of calcium and sodium (Na) are supplied by carbonate weathering and atmospheric input, respectively. The estimated low proportion of Sr produced by carbonate weathering was surprising in a carbonate aquifer, and the 87Sr/86Sr data indicated that the silicate Sr source had low Rb/Sr and 87Sr/86Sr ratios. There was an increase in the maximum δ7Li values in fresh groundwaters (+36‰) relative to the maximum value in rainfall and seawater (ca. +31‰). As clay minerals are undersaturated in fresh groundwaters, this increase may be explained by Li isotope fractionation associated with ion-exchange reactions on clays and iron(oxy)hydroxides. In the more saline groundwaters, the minimum δ7Li values decreased with depth to +14.5‰, suggesting increased silicate mineral dissolution in the deeper aquifer. These results reveal the importance of water-rock interactions in a coastal carbonate aquifer, and demonstrate the usefulness of Li isotopes for tracing weathering reactions in an environmental setting where traditional weathering tracers, such as sodium and Sr isotopes, are less appropriate. Crown Copyright © 2020 Published by Elsevier B.V
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    Tracing organic carbon processes in a shallow coastal sandy aquifer
    (American Geophysical Union (AGU), 2017-12-14) Meredith, KT; Andersen, MS; Baker, AA; O'Carroll, DM; Bryan, E; Zainuddin, NS; Rutlidge, H; McDonough, LK
    Coastal groundwater resources are likely to be impacted by climate change due to changes in recharge patterns, surface water flow and sea-level rise, which all have the potential to change how carbon is transported and stored within a catchment. Large quantities of carbon are currently stored within coastal wetland systems, so understanding carbon dynamics is important for climate change predictions into the future. Furthermore, dissolved organic carbon (DOC) can play a major role in weathering processes and deterioration of water quality, therefore understanding the sources, degradation pathways and its reactivity is important. Groundwater samples were collected from five nested sites (15 wells) from a shallow (0-20m) coastal sandy aquifer system located at Anna Bay, New South Wales, Australia. Surface water samples were also collected from the adjacent wetland. Waters were measured for major ion chemistry, carbon isotopes (δ13CDIC, δ13CDOC and 14CDIC) and tritium (3H). The dissolved organic matter (DOM) character was determined using optical spectroscopy and liquid chromatography. DOC was found to be elevated in the wetland (18 ppm) and had the lowest δ13CDOC value (-30.3 ‰). The shallow (3.5 m) groundwater located closest to but downgradient of the wetland (5 m) had similar characteristics to the wetland sample but contained significantly lower DOC concentrations (5 ppm) and were 1 ‰ more enriched in δ13CDOC values. This suggests that the aquifer is a sink for organic matter and the process fractionates the carbon isotopes. Higher resolution studies are underway to characterise and constrain timescales for the DOC transformation processes.
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    Understanding the carbon cycle in a Late Quaternary-age limestone aquifer system using radiocarbon of dissolved inorganic and organic carbon
    (European Geosciences Union, 2017-04-26) Bryan, E; Meredith, KT; Baker, AA; Andersen, MS; Post, VEA
    Estimating groundwater residence time is critical for our understanding of hydrogeological systems, for groundwater resource assessments and for the sustainable management of groundwater resources. Due to its capacity to date groundwater up to 30 thousand years old, as well as the ubiquitous nature of dissolved carbon (as organic and inorganic forms) in groundwater, 14C is the most widely used radiogenic dating technique in regional aquifers. However, the geochemistry of carbon in groundwater systems includes interaction with the atmosphere, biosphere and geosphere, which results in multiple sources and sinks of carbon that vary in time and space. Identifying these sources of carbon and processes relating to its release or removal is important for understanding the evolution of the groundwater and essential for residence time calculations. This study investigates both the inorganic and organic facets of the carbon cycle in groundwaters throughout a freshwater lens and mixing zone of a carbonate island aquifer and identifies the sources of carbon that contribute to the groundwater system. Groundwater samples were collected from shallow (5-20 m) groundwater wells on a small carbonate Island in Western Australia in September 2014 and analysed for major and minor ions, stable water isotopes (SWIs: δ18O, δ2H), 3H, 14C and 13C carbon isotope values of both DIC and DOC, and 3H. The composition of groundwater DOC was investigated by Liquid Chromatography-Organic Carbon Detection (LC-OCD) analysis. The presence of 3H (0.12 to 1.35 TU) in most samples indicates that groundwaters on the Island are modern, however the measured 14CDIC values (8.4 to 97.2 pmc) suggest that most samples are significantly older due to carbonate dissolution and recrystallisation reactions that are identified and quantified in this work. 14CDOC values (46.6 to 105.6 pMC) were higher than 14CDIC values and were well correlated with 3H values, however deeper groundwaters had lower 14CDOC values than expected. LC-OCD chromatography of these groundwaters were found to contain higher concentrations of humic substances, that are most likely attributed to the presence of paleosol horizons at depth in the limestone, which are a common feature in aeolianite deposits along the Western coast of Australia and are related to Quaternary sea level change. The paleosols likely contribute old organic matter to the deeper groundwaters, which may explain the lower 14CDOC values. This study has shown that a combined approach that utilises both DIC and DOC tracers, as well as 3H, is required to identify the sources and evolution of carbon in a groundwater system, as well as the processes that effect the application of 14C dating to groundwaters within a carbonate aquifer. © 2017 Author(s). CC Attribution 3.0 License.