Browsing by Author "Baker, AA"

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    A 35 ka record of groundwater recharge in south-west Australia using stable water isotopes
    (Elsevier B. V., 2020-05-15) Priestley, SC; Meredith, KT; Treble, PC; Cendón, DI; Griffiths, AD; Hollins, SE; Baker, AA; Pigois, JP
    The isotopic composition of groundwater can be a useful indicator of recharge conditions and may be used as an archive to infer past climate variability. Groundwater from two largely confined aquifers in south-west Australia, recharged at the northernmost extent of the westerly wind belt, can help constrain the palaeoclimate record in this region. We demonstrate that radiocarbon age measurements of dissolved inorganic carbon are appropriate for dating groundwater from the Leederville aquifer and Yarragadee aquifer within the Perth Basin. Variations in groundwater δ18O values with mean residence time were examined using regional and flow line data sets, which were compared. The trends in the regional groundwater data are consistent with the groundwater flow line data supporting the hypothesis that groundwater δ18O is a robust proxy for palaeo-recharge in the Perth Basin. A comparison between modern groundwater and rainfall water isotopes indicates that recharge is biased to months with high volume and/or intense rainfall from the westerly wind circulation and that this has been the case for the last 35 ka. Lower stable water isotope values are interpreted to represent recharge from higher volume and/or more intense rainfall from 35 ka through the Last Glacial Maximum period although potentially modulated by changes in recharge thresholds. The Southern Perth Basin groundwater isotopic record also indicates a trend towards higher volume and/or intense rainfall during the Mid- to Late Holocene. The long-term stable water isotope record provides an understanding of groundwater palaeo-recharge. Knowledge of recharge dynamics over long time scales can be used to improve current water sharing plans and future groundwater model predictions. © Crown Copyright 2019
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    A 35 ka record of groundwater recharge using stable water isotopes for Perth Basin in south-west Australia
    (National Centre for Groundwater Research And Training, & Australian Chapter International Association Of Hydrogeologists, 2019-11-25) Priestley, SC; Meredith, KT; Treble, PC; Cendón, DI; Griffiths, AD; Hollins, SE; Baker, AA; Pigois, JP
    Objectives: As most large groundwater basins can contain ‘old’ groundwater where extraction exceeds groundwater recharge, knowledge of the past conditions and timing under which groundwater was recharged is needed to sustainably manage groundwater resources. Moreover, the isotopic composition of groundwater can be a useful indicator of rainfall isotope compositions and help to determine the drivers and impacts of rainfall and climate change. Applying isotopic tools to groundwater contained in regional aquifer systems can provide low-resolution information on recharge intensity, recharge source and past climatic conditions for the region. Design and Methodology: A dataset containing groundwater ages (14CDIC) and stable isotopes of water (δ18O and δ2H) from two regional groundwater systems within the Perth Basin, the Leederville Formation and Yarragadee Formation, were compiled to create a low-resolution palaeo-archive of groundwater recharge. Original data and results: The trends in stable isotopes of water over time in the regional groundwater data are consistent with groundwater flow line data supporting our hypothesis that groundwater stable isotopes are a proxy for palaeo-recharge. A comparison between modern groundwater and rainfall water isotopes indicates that recharge is biased to months with high volume and/or intense rainfall from the westerly wind circulation and that this has been the case for the last 35 ka. Lower stable water isotope values are interpreted to represent recharge from higher volume and/or more intense rainfall from 35 ka through the Last Glacial Maximum period although potentially modulated by changes in recharge thresholds. Conclusion: The groundwater isotope record is interpreted to be a low-resolution archive of recharge driven by changes in the relative intensity of past rainfall and recharge thresholds. This long-term stable isotopic recharge record provides a greater understanding of groundwater palaeo-recharge, and the connection between recharge and climate in the past. © The Authors
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    Assessing connectivity between an overlying aquifer and a coal seam gas resource using methane isotopes, dissolved organic carbon and tritium
    (Nature, 2015-11-04) Iverach, CP; Cendón, DI; Hankin, SI; Lowry, D; Fisher, RE; France, JL; Nisbet, EG; Baker, AA; Kelly, BFJ
    Coal seam gas (CSG) production can have an impact on groundwater quality and quantity in adjacent or overlying aquifers. To assess this impact we need to determine the background groundwater chemistry and to map geological pathways of hydraulic connectivity between aquifers. In south-east Queensland (Qld), Australia, a globally important CSG exploration and production province, we mapped hydraulic connectivity between the Walloon Coal Measures (WCM, the target formation for gas production) and the overlying Condamine River Alluvial Aquifer (CRAA), using groundwater methane (CH4) concentration and isotopic composition (δ13C-CH4), groundwater tritium (3H) and dissolved organic carbon (DOC) concentration. A continuous mobile CH4 survey adjacent to CSG developments was used to determine the source signature of CH4 derived from the WCM. Trends in groundwater δ13C-CH4 versus CH4 concentration, in association with DOC concentration and 3H analysis, identify locations where CH4 in the groundwater of the CRAA most likely originates from the WCM. The methodology is widely applicable in unconventional gas development regions worldwide for providing an early indicator of geological pathways of hydraulic connectivity. © The Authors. This work is licensed under a Creative Commons Attribution 4.0 International Licence. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons licence, users will need to obtain permission from the licence holder to reproduce the material.
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    Assessing connectivity between an overlying aquifer and a coal seam gas resource using methane isotopes, dissolved organic carbon and tritium
    (National Centre for Groundwater Research And Training, 2015-11-03) Iverach, CP; Cendón, DI; Hankin, SI; Lowry, D; Fisher, RE; France, JL; Nisbet, EG; Baker, AA; Kelly, BFJ
    Coal seam gas (CSG) production can have an impact on groundwater quality and quantity in adjacent or overlying aquifers. To assess this impact we need to determine the background groundwater chemistry and to map geological pathways of hydraulic connectivity between aquifers. In south-east Queensland (Qld), Australia, a globally important CSG exploration and production province, we mapped hydraulic connectivity between the Walloon Coal Measures (WCM, the target formation for gas production) and the overlying Condamine River Alluvial Aquifer (CRAA), using groundwater methane (CH4) concentration and isotopic composition (δ13C-CH4), groundwater tritium (3H) and dissolved organic carbon (DOC) concentration. A continuous mobile CH4 survey adjacent to CSG developments was used to determine the source signature of CH4 derived from the WCM. Trends in groundwater δ13C-CH4 versus CH4 concentration, in association with DOC concentration and 3H analysis, identify locations where CH4 in the groundwater of the CRAA most likely originates from the WCM. The methodology is widely applicable in unconventional gas development regions worldwide for providing an early indicator of geological pathways of hydraulic connectivity. © The Authors.
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    Assessing the hydraulic connection between fresh water aquifers and unconventional gas production using methane and stable isotopes
    (European Geosciences Union, 2015-04-12) Iverach, CP; Cendón, DI; Hankin, SI; Lowry, D; Fisher, RE; France, JL; Nisbet, EG; Baker, AA; Kelly, BFJ
    Unconventional gas developments pose a risk to groundwater quality and quantity in adjacent or overlying aquifers. To manage these risks there is a need to measure the background concentration of indicator groundwater chemicals and to map pathways of hydraulic connectivity between aquifers. This study presents methane (CH4) concentration and isotopic composition, dissolved organic carbon concentration ([DOC]) and tritium (3H) activity data from an area of expanding coal seam gas (CSG) exploration and production (Condamine Catchment, south-east Queensland, Australia). The target formation for gas production within the Condamine Catchment is the Walloon Coal Measures (WCM). This is a 700 m thick, low-rank CSG resource, which consists of numerous thin discontinuous lenses of coal separated by very fine-to medium-grained sandstone, siltstone, and mudstone, with minor calcareous sandstone, impure limestone and ironstone. The thickness of the coal makes up less than 10% of the total thickness of the unit. The WCM are overlain by sandstone formations, which form part of the Great Artesian Basin (GAB). The Condamine Alluvium fills a paleo-valley carved through the above formations. A combination of groundwater and degassing air samples were collected from irrigation bores and government groundwater monitoring boreholes. Degassing air samples were collected using an SKC 222-2301 air pump, which pumped the gas into 3 L Tedlar bags. The groundwater was analysed for 3H and [DOC]. A mobile CH4 survey was undertaken to continuously sample air in and around areas of agricultural and unconventional gas production. The isotopic signature of gas from the WCM was determined by sampling gas that was off-gassing from a co-produced water holding pond as it was the largest emission that could be directly linked to the WCM. This was used to determine the source signature of the CH4 from the WCM. We used Keeling plots to identify the source signature of the gas sampled. For the borehole samples these plots assume that there are only two sources of CH4, each with a unique isotopic signature. When the two sources mix in varying proportions they will plot along a straight line in the Keeling plot. Geometric mean displacement was used to fit a regression line and determine the intercept value. Within the Keeling plot, samples clustered according to their 3H and [DOC] values. One cluster is associated with near surface biological processes, while the other cluster can be attributed to gas sourced from the WCM. This indicates that in places there is hydraulic connectivity between the WCM and the overlying Condamine Alluvium. The results from this case study demonstrate that measuring 3H activity, [DOC] and CH4 concentrations in combination with CH4 isotopic analysis can provide an early indicator of hydraulic connectivity in areas of expanding unconventional gas development. © Author(s) 2015. CC Attribution 3.0 License.
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    Carbon cycling in sub-Antarctic and Antarctic lakes
    (American Geophysical Union (AGU), 2021-12-17) McDonough, LK; Meredith, KT; Saunders, KM; Baker, AA
    Between 2000 and 2010, anthropogenic carbon emissions rose at rates of 2.2% year-1, a 70% increase above the annual rates observed between 1970 and 2000. This has accelerated global temperature increases. As a result, carbon fluxes to and from aquatic environments have changed, affecting microbial community compositions, and impacting the ability of some environments to act as carbon stores. Whilst the factors influencing nutrient cycling in many aquatic environments, including major rivers and oceans, have been well studied, little is known about the biogeochemical processes driving aquatic carbon cycling in sub-Antarctic and Antarctic lakes, and how this may be impacted by climate change. This is in part because sampling programs designed for such isolated environments take years to plan and require international collaboration. The isolation of these lakes however mean that many are relatively undisturbed by human activities, making them ideal locations to study the interactions between hydrological and biogeochemical processes, and the impact of climate change on natural carbon sources, transformation and storage. We aim to analyse Antarctic and sub-Antarctic lake water using organic carbon characterisation techniques such as fluorescence, liquid chromatography organic carbon detection and synchrotron characterisation, as well as radiocarbon and stable carbon isotopes of dissolved organic carbon (14CDOC and 13CDOC) and dissolved inorganic carbon (14CDIC and 13CDIC). This will allow us to identify key carbon sources such as terrestrial vegetation, groundwater and permafrost thaw, carbon age, and cycling via biodegradation or other processing mechanisms. The data collected for this project will form the first comprehensive spatial and temporal survey of dissolved carbon in both organic and inorganic phases in lakes across the region, aimed at understanding present-day environmental processes and their drivers. These data also have the potential to calibrate palaeo-records such as peat and lake archives which will assist in the understanding of the impacts of large-scale climate variability and environmental changes that may occur in the future.
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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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    Cave drip water solutes in south-eastern Australia: constraining sources, sinks and processes
    (Elsevier, 2019-02-15) Tadros, CV; Treble, PC; Baker, AA; Hankin, SI; Roach, R
    Constraining sources and site-specific processes of trace elements in speleothem geochemical records is key to an informed interpretation. This paper examines a 10-year data set of drip water solutes from Harrie Wood Cave, south-eastern Australia, and identifies the processes that control their response to El Niño-Southern Oscillation events which varies the site water balance. The contributions of aerosol and bedrock end-members are quantified via hydrochemical mass balance modelling. The parent bedrock is the main source for the drip water solutes: Mg, Sr, K and trace elements (Ba, Al, V, Cr, Mn, Ni, Co, Cu, Pb and U), while atmospheric aerosol inputs also contribute significantly to drip water trace elements and Na, K and Zn. A laboratory investigation evaluating water-soluble fractions of metals in soil samples and soil enrichment factors provided a basis for understanding metal retainment and release to solution and transport from the soil zone. These results identified the role of the soil as a sink for: trace metals, Na and K, and a secondary source for Zn. Further, soil processes including: cation exchange, K-fixation, metal adsorption to colloids and the release of Zn associated with organic matter degradation further modify the chemical composition of the resultant drip waters. This research is significant for the south-eastern Australian region, as well as other sites in a karst setting with clay-rich soil. In particular these results reveal that the response of drip water chemistry to hydroclimatic forcing is non-linear, with the greatest response observed when the long-term gradient in the cumulative water balance reverses. This longer-term drip water monitoring dataset is significant because it provides the pivotal framework required to reliably identify suitable trace element proxies for interpretation in geochemical speleothem records on multi-decadal timescales. © 2018 Crown Copyright © 2018 Published by Elsevier B.V.
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    Cave monitoring to constrain the paleoclimate interpretation of δ18O proxy in speleothems from semi-arid areas
    (University of New South Wales and Australian Nuclear Science and Technology Organisation, 2015-07-09) Markowska, M; Baker, AA; Andersen, MS; Jex, CN; Cuthbert, MO; Rau, GC; Graham, PW; Rutlidge, H; Mariethoz, G; Marjo, CE; Treble, PC; Edwards, N
    Not supplied to the ANSTO Library.
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    Cave stalagmites as records of past recharge frequency in semi-arid Australia
    (National Centre for Groundwater Research And Training, 2015-11-03) Markowska, M; Baker, AA; Andersen, MS; Rutlidge, H; Jex, CN; Cuthbert, MO; Rau, GC; Adler, L; Graham, PW; Mariethoz, G; Marjo, CE; Treble, PC
    Understanding past variability in groundwater recharge over recent time scales (0 – 10 ka) in Australia is essential for future sustainable groundwater management in a changing climate. Currently, there are limited data about past infiltration rates and their relationship to environmental controls that dominate recharge variability. Speleothem (cave precipitates) records may provide a new approach to understanding past infiltration (i.e. recharge rates), in addition to traditional interpretations of connectivity between climate and the hydrological cycle, in drier parts of Australia. In this study we used Cathedral Cave, (SE Australia) located in a temperate semi-arid climate, as a natural laboratory to investigate cave infiltration rates and the climate-karst-cave interactions driving the isotopic (δ18O) and chemical variability in modern drip water. These findings were then used to interpret the δ18O stalagmite record from two modern speleothems growing during the last ~50 years. Modern drip water results showed that the δ18O composition was enriched by up to 2.77 ‰ relative to annually weighted mean rainfall. Isotopically lighter δ18O occurred during infiltration events, followed by subsequent isotopic enrichment as evaporation in the unsaturated zone fractionated δ18O of stored water. Drip rate monitoring revealed that larger events leading to infiltration were infrequent (0 – 3 a-1) and the ‘effectiveness’ of these infiltration events was controlled by antecedent moisture conditions in the soil zone. In drier climatic zones, evaporation drives the enrichment of δ18O in the unsaturated zone, allowing periods of infiltration to be identified from the stable isotopic composition of drip waters. Our findings are important for interpreting speleothem records from regions with infrequent recharge and high evaporation rates. Such records are likely to contain evidence of past infiltration events moderated by an evaporation signal, allowing records of paleo-recharge to be reconstructed for drier climate regions of Australia.
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    Caves demonstrate decrease in rainfall recharge of southwest Australian groundwater is unprecedented for the last 800 years
    (Springer Nature, 2023-06-09) Priestley, SC; Treble, PC; Griffiths, AD; Baker, AA; Abram, NJ; Meredith, KT
    Billions of people worldwide rely on groundwater. As rainfall in many regions in the future is projected to decrease, it is critical to understand the impacts of climate change on groundwater recharge. The groundwater recharge response to a sustained decrease in rainfall across southwest Australia that began in the late 1960s was examined in seven modern speleothems and drip waters from four caves. These show a pronounced increase or uptick in regional drip water and speleothem oxygen isotopic composition (δ18O) that is not driven by a change in rainfall δ18O values, but is in response to the shallow karst aquifers becoming disconnected from rainfall recharge due to regional drying. Our findings imply that rainfall recharge to groundwater may no longer be reliably occurring in this region, which is highly dependent on groundwater resources. Examination of the longer speleothem record shows that this situation is unprecedented over the last 800 years. © The Authors - Open Access licensed under a Creative Commons Attribution 4.0 International Licence.
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    Caves provide early warning of unprecedented decrease in rainfall recharge of groundwater
    (Research Square, 2022-05-02) Priestley, SC; Treble, PC; Griffiths, AD; Baker, AA; Abram, NJ; Meredith, KT
    Billions of people worldwide rely on groundwater. As rainfall in many regions in the future is projected to decrease, it is critical to understand the impacts of climate change on groundwater recharge. In this study, five caves record a consistent response to a sustained decrease in rainfall across southwest Australia that began in the late 1960s, characterised by a pronounced increase or ’uptick’ in dripwater and speleothem oxygen isotopic composition (δ18O). It is demonstrated that the uptick is in response to the shallow karst aquifers becoming disconnected from recharge due to regional drying. Our findings imply that rainfall recharge to groundwater across this region is no longer reliably occurring. Examination of the longer speleothem record shows that this is unprecedented over at least the last 800 years. A global network of cave dripwater monitoring would serve as an early warning of reduced groundwater recharge elsewhere, while evidence for upticks in speleothem paleoclimate records would provide a longer-term context to evaluate if current groundwater recharge changes are outside the range of natural variability. This study also validates speleothems as recorders of past hydroclimate via amplification of the δ18O signal by karst hydrology highlighting that speleothem δ18O are records of recharge, rather than a direct proxy for rainfall. © 2022 The Authors
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    Caves: observatories of Australia’s diffuse groundwater recharge history
    (National Centre for Groundwater Research And Training, 2015-11-03) Baker, AA; Treble, PC; Andersen, MS; Markowska, M; Coleborn, K; Flemons, I; Kempsey Speleological Society
    Quantifying the timing and extent of diffuse groundwater recharge is crucial for our understanding of groundwater recharge processes. However, diffuse recharge is notably difficult to quantify. Our novel approach is to use caves as natural observatories of the diffuse recharge process, with the aim of improving our understanding of diffuse recharge in the context of climate change and climate variability. Since 2010, funded by the NCRIS Groundwater Infrastructure project, researchers from UNSW and ANSTO have established a long-term, national monitoring program of infiltration into caves using automated loggers. Five karst regions, in semi-arid, temperate, subtropical and montane climates from southwest WA to the mid- north coast of NSW, have been instrumented with automatic infiltration loggers. Over 200 loggers (between 10 and 40 per cave) have collected data on the timing and amount of diffuse recharge, from sites of contrasting limestone geology, starting in 2010. We present empirical data on the timing and relative amounts of diffuse recharge from 2010 to present. Caves with a range of depths from 0-40m show decreasing frequency of diffuse recharge events with depth below ground surface. Event-based rainfall intensity is confirmed to be the primary driver of diffuse groundwater recharge at all fractured rock sites, whereas annual rainfall amount is the primary driver at a site with high primary porosity. Inter-annual variability in the frequency and relative amount of recharge is compared to climate forcing variables such as the ENSO and surface temperature. Groundwater recharge is via both direct (river recharge) and diffuse processes. With anthropogenic global warming, increased temperatures will increase evaporation, and will likely change ENSO patterns, both of which will affect diffuse groundwater recharge. Our cave observatory system helps improve our understanding of the diffuse recharge process and provides a baseline monitoring network during a period of climate change.
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    Changes in global groundwater organic carbon driven by climate change and urbanization
    (Springer Nature, 2020-03-09) McDonough, LK; Santos, IR; Andersen, MS; O'Carroll, DM; Rutlidge, H; Meredith, KT; Oudone, PP; Bridgeman, J; Gooddy, DC; Sorensen, JPR; Lapworth, DJ; MacDonald, AM; Ward, J; Baker, AA
    Climate change and urbanization can increase pressures on groundwater resources, but little is known about how groundwater quality will change. Here, we use a global synthesis (n = 9,404) to reveal the drivers of dissolved organic carbon (DOC), which is an important component of water chemistry and substrate for microorganisms that control biogeochemical reactions. Dissolved inorganic chemistry, local climate and land use explained ~ 31% of observed variability in groundwater DOC, whilst aquifer age explained an additional 16%. We identify a 19% increase in DOC associated with urban land cover. We predict major groundwater DOC increases following changes in precipitation and temperature in key areas relying on groundwater. Climate change and conversion of natural or agricultural areas to urban areas will decrease groundwater quality and increase water treatment costs, compounding existing constraints on groundwater resources. © 2020, The Author(s)
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    Changes in groundwater dissolved organic matter character in a coastal sand aquifer due to rainfall recharge
    (Elsevier, 2020-02-01) McDonough, LK; O'Carroll, DM; Meredith, KT; Andersen, MS; Brügger, C; Huang, HX; Rutlidge, H; Behnke, MI; Spencer, RGM; McKenna, AM; Marjo, CE; Oudone, PP; Baker, AA
    Dissolved organic matter (DOM) in groundwater is fundamentally important with respect to biogeochemical reactions, global carbon cycling, heavy metal transport, water treatability and potability. One source of DOM to groundwater is from the transport of organic matter from the vadose zone by rainfall recharge. Changes in precipitation patterns associated with natural climate variability and climate change are expected to alter the load and character of organic matter released from these areas, which ultimately impacts on groundwater quality and DOM treatability. In order to investigate potential changes in groundwater DOM character after rainfall recharge, we sampled shallow groundwater from a coastal peat-rich sand aquifer in New South Wales, Australia, during an extended period of low precipitation (average daily precipitation rate < 1.6 mm day−1 over the 8 months prior to sampling), and after two heavy precipitation events (84 mm day−1 and 98 mm day−1 respectively). We assess changes in DOM composition after correcting for dilution by a novel combination of two advanced analytical techniques: liquid chromatography organic carbon detection (LC-OCD) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We also assess changes in water chemistry pre- and post-rainfall. Post-rainfall, we show that the dilution-corrected amount of highly aromatic DOM molecular formulae (i.e. those categorised into the groups polyphenolics and condensed aromatics) were 1.7 and 2.0 times higher respectively than in pre-rainfall samples. We attribute this to the flushing of peat-derived DOM from buried organic material into the groundwater. We also identify that periods of low precipitation can lead to low hydrophilic/HOC ratios in groundwater (median = 4.9, n = 14). Redundancy analysis (RDA) was used to compare the HOC fraction with FT-ICR MS compound groups. We show that HOC has a more aromatic character in pre-rainfall samples, and is less similar to the aromatic groups in post-rainfall samples. This suggests that the decline in water-borne hydrophobics observed post-rainfall could be associated with preferential adsorption of the hydrophobic aromatic DOM, making post-rainfall samples less treatable for potable water supply. Post-rainfall we also observe significant increases in arsenic (leading to concentrations greater than 3 times the World Health Organisation drinking water limit of 10 μg / L). Increases in coastal rainfall due to climate change may therefore alter the composition of groundwater DOM in coastal peatland areas in ways that may impact DOM bioavailability, and increase arsenic concentrations, reducing the ease of water treatment for human consumption. To the best of our knowledge, this is the first study to identify the chemical and molecular changes of shallow groundwater DOM pre-rainfall and post-rainfall in a sedimentary organic carbon rich environment through multiple analytical techniques. © 2019 Elsevier Ltd
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    Characterisation and controls on mineral-sorbed organic matter from a variety of groundwater environments
    (EarthArXiv, 2019-12-13) Oudone, PP; Rutlidge, H; Andersen, MS; O'Carroll, DM; Cheong, S; Meredith, KT; McDonough, LK; Marjo, CE; Baker, AA
    Detailed investigations into natural groundwater organic matter (OM) as carbon sources or sinks in the natural carbon cycle are generally limited. Groundwater OM concentration and composition is altered by biodegradation and sorption to minerals. In the saturated zone of an aquifer, dissolved organic matter (DOM) may represent a significant fraction of the natural groundwater dissolved organic carbon (DOC) pool, therefore understanding how mineral sorption influences OM will contribute to our understanding of how DOC is processed in groundwater. In this study we investigate the dominant fractions of natural DOC in groundwater and the extent of sorption on three common minerals found in the environment: iron-oxide coated sand, calcite and quartz sand. DOM sorption on these minerals was studied using groundwaters from three different geological environments in New South Wales, Australia: Anna Bay (quartz-sand coastal aquifer); Maules Creek (alluvial gravel and clay aquifer); and Wellington (alluvial karst limestone aquifer). Each groundwater and surface sample were characterised before and after sorption using size exclusion liquid chromatography with organic carbon detection (LC-OCD). Analysis revealed that humic substances (HS) are the dominant (13 – 70%) fraction of natural groundwater DOC. HS sorption on iron-oxide coated sand was higher than that on calcite and quartz sand, respectively while sorption on the calcite was also higher than on quartz sand. In shallow-sandy aquifer groundwater, due to less DOC sorption in sandy environment (Anna Bay), DOC concentration was found to be the highest compared to that from karst and other alluvial boreholes from Maules Creek and Wellington. HS sorption increases with the mineral mass and DOC concentration indicating that DOC sorption to the mineral surface did not reach saturation under the study conditions. Only the high-DOC alluvial groundwater produced significant sorption to each mineral phase and of the chemical fractions present (85% of 72 batch systems that HS sorption was found). Multiple linear regression showed that mineral mass, mineral type, depth of groundwater sample, DOC concentration, aqueous Fe2+ concentration and DOM aromaticity are the controlling factors of DOC sorption in the various groundwater environments. The regression analysis showed sorption decreases with depth, which could be because of DOC sorption along the groundwater flow path, resulting in less DOC at depth. The multiple linear regression predicts less DOC (HS) sorption in quartz sand system, agreeing with laboratory sorption results. HS sorption also correlated with aromaticity suggesting the chemical character of HS will control the degree of mineral sorption. The model also indicated that DOC sorption is negatively correlated with dissolved Fe2+ concentration in water samples presumably due to redox condition which is under anoxic environment iron oxide became electron acceptors under the process of DOC biodegradation leaving higher Fe2+ concentration and less available DOC for sorption.
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    Characterisation of groundwater dissolved organic matter using LC-OCD: implications for water treatment
    (Elsevier, 2021-01-01) Rutlidge, H; McDonough, LK; Oudone, PP; Andersen, MS; Meredith, KT; Chinu, K; Peterson, MA; Baker, AA
    The polarity and molecular weight of dissolved organic matter (DOM) is an important factor determining the treatability of water for domestic supply. DOM in surface water and groundwater is comprised of a mixture of carbon with varying molecular weight ranges, with its composition driven by DOM sources and processing. Here, we present the largest dataset of chromatographic DOM in surface and groundwater samples (n = 246) using liquid chromatography organic carbon detection (LCsingle bondOCD). Our data represents four categories (surface water, hyporheic zone water, local groundwater, and regional groundwater) from five different sites across Australia. In all environments, high molecular weight hydrophilic DOM such as biopolymers (BP) and humic substances (HS) are present in surface waters and are processed out of groundwater as it moves from surface water and hyporheic zones into shallow local groundwater and deeper regional groundwaters. This results in a higher percentage of low molecular weight neutrals (LMWN) and hydrophobic organic carbon (HOC) in deeper regional groundwaters. Our findings indicate that the presence of sedimentary organic matter strongly influence the character of surface and groundwater DOM, resulting in groundwater with higher HS aromaticity and molecular weight, and reduced percentage of LMWNs. We also observe highly variable hydrophilic / HOC ratios in groundwater at all sites, with 9.60% and 25.64% of samples at sites containing sedimentary peat layers and non-sedimentary peat sites respectively containing only hydrophilic dissolved organic carbon (DOC). We identify average hydrophilic / HOC ratios of 4.35 ± 3.76 and 7.53 ± 5.32 at sites containing sedimentary peat layers and non-sedimentary peat sites respectively where both hydrophilic DOC and HOC are present. Overall our results suggest that fractured rock and alluvial aquifers in sedimentary organic carbon poor environments may contain DOC which is better suited to ozonation, biologically activated carbon filtration powdered activated carbon, suspended ion exchange treatment or magnetic ion exchange resin since DOC is more hydrophilic and of lower molecular weight and lower aromaticity. Aquifers located near sedimentary organic matter layers may benefit from pre-treatment by coagulation/flocculation, sedimentation and sand filtration which have high removal efficiency for high molecular weight and polar compounds. © 2021 Elsevier Ltd.
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    Characterisation of shallow groundwater dissolved organic matter in aeolian, alluvial and fractured rock aquifers
    (Elsevier, 2020-03-15) McDonough, LK; Rutlidge, H; O’Carroll, DM; Andersen, MS; Meredith, KT; Benkhe, MI; Spencer, RGM; McKenna, AM; Marjo, CE; Oudone, PP; Baker, AA
    Groundwater organic matter is processed within aquifers through transformations such as the adsorption of dissolved organic matter (DOM) to minerals and biodegradation. The molecular character of DOM varies according to its source and this can impact its bioavailability and reactivity. Whilst the character of DOM in riverine and oceanic environments is increasingly well understood, the sources, character and ultimately the fate of groundwater DOM remains unclear. Here we examine groundwater DOM from contrasting hydrogeological settings in New South Wales, Australia. For the first time, we identify the distinct molecular composition of three groundwater DOM end-members including a modern terrestrial input, an aged sedimentary peat source, and an aged stable by-product pool. We also identify and characterise the processing pathway of DOM in semi-arid, low sedimentary organic carbon (OC) environments. Based on size exclusion chromatography, ultrahigh-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), isotopic analyses (13C, 14C and 3H) and principle component analysis (PCA), we show that in higher rainfall temperate coastal peatland environments, large amounts of aged sedimentary organic carbon can leach into groundwater resulting in higher molecular weight (500 g mol−1 < molecular weight > 1000 g mol−1) and highly aromatic groundwater DOM with high O/C ratios and low H/C ratios. We show that in semi-arid environments with low rainfall rates and high groundwater residence times, groundwater dissolved organic carbon (DOC) is processed into increasingly low molecular weight (<350 g mol−1), low aromaticity DOM with low O/C ratios and high H/C ratios by subsurface processing mechanisms such as biodegradation and adsorption. We provide the first comprehensive study of groundwater DOM characterisation based on multiple analytical techniques, and highlight the impact of source inputs and processing on groundwater DOM composition at a molecular level. Crown Copyright © 2020 Published by Elsevier Ltd
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    Chemical characterisation and source identification of atmospheric aerosols in the Snowy Mountains, south-eastern Australia
    (Elsevier, 2018-07-15) Tadros, CV; Crawford, J; Treble, PC; Baker, AA; Cohen, DD; Atanacio, AJ; Hankin, SI; Roach, R
    Characterisation of atmospheric aerosols is of major importance for: climate, the hydrological cycle, human health and policymaking, biogeochemical and palaeo-climatological studies. In this study, the chemical composition and source apportionment of PM2.5 (particulate matter with aerodynamic diameters less than 2.5 μm) at Yarrangobilly, in the Snowy Mountains, SE Australia are examined and quantified. A new aerosol monitoring network was deployed in June 2013 and aerosol samples collected during the period July 2013 to July 2017 were analysed for 22 trace elements and black carbon by ion beam analysis techniques. Positive matrix factorisation and back trajectory analysis and trajectory clustering methods were employed for source apportionment and to isolate source areas and air mass travel pathways, respectively. This study identified the mean atmospheric PM2.5 mass concentration for the study period was (3.3 ± 2.5) μg m−3. It is shown that automobile (44.9 ± 0.8)%, secondary sulfate (21.4 ± 0.9)%, smoke (12.3 ± 0.6)%, soil (11.3 ± 0.5)% and aged sea salt (10.1 ± 0.4)% were the five PM2.5 source types, each with its own distinctive trends. The automobile and smoke sources were ascribed to a significant local influence from the road network and bushfire and hazard reduction burns, respectively. Long-range transport are the dominant sources for secondary sulfate from coal-fired power stations, windblown soil from the inland saline regions of the Lake Eyre and Murray-Darling Basins, and aged sea salt from the Southern Ocean to the remote alpine study site. The impact of recent climate change was recognised, as elevated smoke and windblown soil events correlated with drought and El Niño periods. Finally, the overall implications including potential aerosol derived proxies for interpreting palaeo-archives are discussed. To our knowledge, this is the first long-term detailed temporal and spatial characterisation of PM2.5 aerosols for the region and provides a crucial dataset for a range of multidisciplinary research. Crown Copyright © 2018 Published by Elsevier B.V.