Browsing by Author "Marjo, CE"
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- ItemAnomalous tree-ring identification facilitated by AMS 14C analysis in subtropical and tropical Australian Araucariaceae samples enables development of a long-term, high-resolution climate reconstruction(Australian Nuclear Science and Technology Organisation, 2021-11-17) Haines, HA; Palmer, JG; Hua, Q; English, NB; Hiscock, W; Turney, CSM; Marjo, CE; Gadd, PS; Kemp, J; Olley, JMIn Australia the majority of tropical and subtropical regions lack long-term instrumental climate records. Paleoclimate reconstructions from tree rings provide one alternative but very few dendrochronological investigations have so far been undertaken. Early assessments of mainland Australian tree species were discouraging due to the high prevalence of anomalous ring boundaries. Some species, however, were seen as more favourable than others including those in the Araucariaceae family which is common along the subtropical-tropical Australian east coast. These trees are longer lived than many other species in the region and contain growth rings known to be annual in nature and responsive to climatic conditions. There is however, a heavy prevalence of anomalous ring boundaries in species from this family which must be accounted for when dating these species. Here we describe the tree-ring characteristics and growth response from two stands of Hoop pine (Araucaria cunninghamii) trees located in subtropical and tropical Queensland, Australia (regions known for experiencing extreme hydroclimatic events). Confirmation of annual growth driven by moisture sensitivity was determined using radius dendrometers on four trees in Lamington National Park (c. 28º S). Tree cores were collected from both the Lamington stand as well as a stand at Hidden Valley near Paluma, Queensland (c. 19º S). Ring-width assessment showed the presence of false, faint, locally absent, and wedging rings in both sites. Results of bomb-pulse radiocarbon dating of selected single tree rings demonstrated that trees from this species can fall into one of three categories: A – those with locally-absent rings around the circumference of the trees, B – those where false rings were observed, and C – those with many wedging and locally-absent rings. Only trees in the first two categories were able to be included in the master chronologies. Traditional dendrochronological analysis with age validation by bomb-pulse radiocarbon dating allowed for a robust ring-width chronology from 1805-2014 CE to be developed for the Lamington National Park site. Growth-climate analysis of the master tree-ring chronology determined that the strongest environmental correlation was to wet season drought conditions. The strength of this response was compared to local and regional drought indices as well as to a long-term drought reconstruction. The combined analysis led to the development of a 200-year drought reconstruction for the region which shows influences from both the El Niño Southern Oscillation and the Interdecadal Pacific Oscillation. © The Authors
- ItemThe application of pollen radiocarbon dating and bayesian age-depth modeling for developing robust geochronological frameworks of wetland archives(Cambridge University Press for the Arizona Board of Regents on behalf of the University of Arizona, 2022-04-27) Cadd, HR; Sherborne-Higgins, B; Becerra-Valdivia, L; Tibby, J; Barr, C; Forbes, MS; Cohen, TJ; Tyler, JJ; Vandergoes, MJ; Francke, A; Lewis, RJ; Jacobsen, GE; Marjo, CE; Turney, CSM; Arnold, LJWetland sediments are valuable archives of environmental change but can be challenging to date. Terrestrial macrofossils are often sparse, resulting in radiocarbon (14C) dating of less desirable organic fractions. An alternative approach for capturing changes in atmospheric 14C is the use of terrestrial microfossils. We 14C date pollen microfossils from two Australian wetland sediment sequences and compare these to ages from other sediment fractions (n = 56). For the Holocene Lake Werri Berri record, pollen 14C ages are consistent with 14C ages on bulk sediment and humic acids (n = 14), whilst Stable Polycyclic Aromatic Carbon (SPAC) 14C ages (n = 4) are significantly younger. For Welsby Lagoon, pollen concentrate 14C ages (n = 21) provide a stratigraphically coherent sequence back to 50 ka BP. 14C ages from humic acid and >100 µm fractions (n = 13) are inconsistent, and often substantially younger than pollen ages. Our comparison of Bayesian age-depth models, developed in Oxcal, Bacon and Undatable, highlight the strengths and weaknesses of the different programs for straightforward and more complex chrono-stratigraphic records. All models display broad similarities but differences in modeled age-uncertainty, particularly when age constraints are sparse. Intensive dating of wetland sequences improves the identification of outliers and generation of robust age models, regardless of program used. © The Author(s), 2022. Published by Cambridge University Press for the Arizona Board of Regents on behalf of the University of Arizona
- ItemCave 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, NNot supplied to the ANSTO Library.
- ItemCave 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, PCUnderstanding 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.
- ItemChanges 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, AADissolved 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
- ItemCharacterisation 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, AADetailed 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.
- ItemCharacterisation 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, AAGroundwater 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
- ItemDripwater organic matter and trace element geochemistry in a semi-arid karst environment: Implications for speleothem paleoclimatology(Elsevier, 2014-06-15) Rutlidge, H; Baker, AA; Marjo, CE; Andersen, MS; Graham, PW; Cuthbert, MO; Jex, CN; Rau, GC; Roshan, H; Markowska, M; Mariethoz, GA series of four short-term infiltration experiments which revealed hydrochemical responses relevant to semi-arid karst environments were carried out above Cathedral Cave, Wellington, New South Wales (NSW), Australia. Dripwater samples were collected at two sites for trace element and organic matter analysis. Organic matter was characterised using fluorescence and interpreted using a PARAFAC model. Three components were isolated that represented unprocessed, soil-derived humic-like and fulvic-like material, processed humic/fulvic-like material and tryptophan-like fluorescence. Principal Component Analysis (PCA) performed on the entire dataset comprising trace element concentrations and PARAFAC scores revealed two dominant components that were identified as soil and limestone bedrock. The soil component was assigned based on significant contributions from the PARAFAC scores and additionally included Ba, Cu, Ni and Mg. The bedrock component included the expected elements of Ca, Mg and Sr as well as Si. The same elemental behaviour was observed in recent stalagmite growth collected from the site. Our experiments demonstrate that existing paleoclimate interpretations of speleothem Mg and Sr, developed in regions of positive water balance, are not readily applicable to water limited environments. We provide a new interpretation of trace element signatures unique to speleothems from water limited karst environments. © 2014, Elsevier Ltd.
- ItemEvaporative cooling of speleothem drip water(Nature Publishing Group, 2014-06-04) Cuthbert, MO; Rau, GC; Andersen, MS; Roshan, H; Rutlidge, H; Marjo, CE; Markowska, M; Jex, CN; Graham, PW; Mariethoz, G; Acworth, RI; Baker, AAThis study describes the first use of concurrent high-precision temperature and drip rate monitoring to explore what controls the temperature of speleothem forming drip water. Two contrasting sites, one with fast transient and one with slow constant dripping, in a temperate semi-arid location (Wellington, NSW, Australia), exhibit drip water temperatures which deviate significantly from the cave air temperature. We confirm the hypothesis that evaporative cooling is the dominant, but so far unattributed, control causing significant disequilibrium between drip water and host rock/air temperatures. The amount of cooling is dependent on the drip rate, relative humidity and ventilation. Our results have implications for the interpretation of temperature-sensitive, speleothem climate proxies such as delta O-18, cave microecology and the use of heat as a tracer in karst. Understanding the processes controlling the temperature of speleothem-forming cave drip waters is vital for assessing the reliability of such deposits as archives of climate change. © 2014, Nature Publishing Group.
- ItemExtent and characterisation of natural groundwater organic matter sorption onto minerals(Copernicus GmbH, 2019-04-08) Oudone, PP; Mustonen, O; Marjo, CE; Meredith, KT; McDonough, LK; Rutlidge, H; Andersen, MS; O'Carroll, DM; Baker, AARivers and aquifers have been proven to be physiochemically connected. Despite their interaction, organic matter (OM) concentration in groundwater is much lower than rivers. One might ask where it goes. For example, is sorption responsible for this missing fraction? If so, what components of OM are utilised by groundwater sorption to the minerals? This research aims to quantify the sorption of natural groundwater DOC over a range of groundwater and surface water environments in South East Australia. Batch experiments were set up by adding 40 ml of filtered (0.22 m) sample to a range of masses of three types of sterilised minerals: iron coated sand, quartz sand and calcium carbonate. The systems were rotated for 1 hour under controlled conditions before analysis by Liquid Chromatography-Organic Carbon Detection (LC-OCD) for the aqueous phase and X-ray Photoelectron Spectroscopy (XPS) for the solid phase. Size-exclusion chromatography using LC-OCD is used to determine the remaining chemical fractions in solution. LC-OCD separates DOC into biopolymers (»20,000 g/mol), humic substances ( 1000 g/mol), building blocks (300-500 g/mol), low molecular weight neutrals (<350 g/mol) and low molecular weight acids (350 g/mol). The technique also provides measures of humic substances aromaticity and relative molecular weight. XPS is used to characterise the surface chemistry of the adsorbed organic layer in terms of the relative carbon, nitrogen, and oxygen content, and the types of chemical bonding. The results of solid-phase XPS is compared with the remaining chemical fractions in solution characterised by LC-OCD. LC-OCD results showed that humic substances were highest in concentration in the groundwater DOC compared to other fractions (13-65%) and was the significant sorbing fraction for all mineral types and water samples. The sorption extent ranges between 4-61%. This sorption was highest for iron coated sand (8-61%) followed by calcium carbonate (10-35%) and then quartz sand (4-22%). XPS showed that more sorbed organics (O, C and N) were found on iron coated sand and calcium carbonate compared to quartz sand. The extent of humic substance sorption was found proportional to its aromaticity and molecular weight for all mineral types and water samples. In conclusion, even though sediment types influence groundwater DOC sorption, the result suggests that groundwater DOM sorption plays an important role in the missing fraction of groundwater DOC (31-9/4%). © Author(s) 2019. CC Attribution 4.0 license.
- ItemFactors affecting dissolved organic carbon in coastal groundwater systems(National Centre for Groundwater Research And Training, 2017-07-11) McDonough, LK; O'Carroll, DM; Andersen, MS; Meredith, KT; Rutlidge, H; Oudone, PP; Marjo, CE; Baker, AABalancing the terrestrial global carbon budget has proven to be a significant challenge. Whilst the movement of carbon in the atmosphere and riverine waters has been extensively studied, the potential for organic carbon to desorb/adsorb from mineral surfaces and act as a groundwater organic carbon source/sink, is poorly understood. To investigate the biodegradable component of groundwater dissolved organic carbon (DOC), groundwater samples were collected from six wells located on Rottnest Island, WA. Wells were selected to cover a range of DOC ages and concentrations in a carbonate aquifer. Water quality parameters such as pH, electrical conductivity, temperature, dissolved oxygen were measured in the field. Samples were analysed for their biodegradable DOC content using spectrofluorometric techniques at set intervals within a 28 day period. Further to this, we examined the conditions and processes affecting DOC at a coastal wetland in Anna Bay, NSW. Four multilevel samplers (MLS’s) were installed in a transect with 1m spacing, with a distance of up to 3 m from the wetland edge. Two samples were taken from each MLS and analysed for DOC, dissolved inorganic carbon (DIC), anions and cations using LC-OCD, spectrofluorometry, UV-Vis and FIA techniques. This research forms part of an ongoing project which will assist in identifying the factors affecting the mobilisation, transport and removal of DOC in uncontaminated groundwater. By quantifying the processes, we can then determine whether the groundwater is a carbon source or sink. Importantly, this information will help guide policy and identify the need to include groundwater resources as part of the carbon economy.
- ItemFire-induced shifts in stalagmite organic matter mapped using synchrotron infrared microspectroscopy(Elsevier, 2024-09) McDonough, LK; Campbell, M; Treble, PC; Marjo, CE; Frisia, S; Vongsvivut, JP; Klein, AR; Kovacs-Kis, V; Baker, AAUnderstanding organic matter (OM) in cave mineral deposits (speleothems) is essential for interpreting land use and climatic changes, and the incorporation of trace elements associated with organic compounds. However, the sources and composition of OM in speleothems are poorly understood due to challenges associated with measuring OM at low concentrations and the destructive nature of most speleothem OM analysis techniques. Synchrotron Fourier-transform infrared (FTIR) microspectroscopy is a promising non-destructive technique that can be used to investigate stalagmite OM composition. We use FTIR to analyse vegetation, soil, calcium carbonate and ash end-members and demonstrate the use of Synchrotron infrared microspectroscopy (IRM) mapping to detect temporal changes in the OM composition of a stalagmite from a shallow cave in south-west Western Australia. Our analysis reveals predominant FTIR peaks in the stalagmite linked to amides and CH2 groups, suggesting potential microbial contributions, with smaller proportions of aromatic, CH3 and Cdouble bondO groups. High-resolution transmission electron microscopy revealed that this OM is likely hosted in sets of nanopores spaced hundreds of nanometers apart, aligned along calcite crystallographic orientations. Furthermore, we assess the impact of known wildfire events as discrete short term environmental changes on the stalagmite’s OM composition. The temporal variability in OM functional group composition after fires implies complex fire-soil-vegetation-microbial interactions. This research demonstrates the effectiveness of Synchrotron IRM mapping in providing insights into the short and long-term environmental influences on stalagmite OM composition. Expanding this research to other regions and climates could further enhance the interpretation of OM changes in speleothem-based palaeoclimate reconstructions. © Crown Copyright © 2024 Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
- ItemGroundwater organic matter: carbon source or sink?(National Centre for Groundwater Research And Training, 2017-07-11) Rutlidge, H; Andersen, MS; O'Carroll, DM; Oudone, PP; McDonough, LK; Meredith, KT; Marjo, CE; Baker, AAThe natural environment plays a critical role in offsetting the anthropogenic carbon emissions. Despite the size of the global groundwater store the processes controlling the concentration and characteristics of organic matter in groundwater are poorly understood. Through a survey of global carbon concentrations, it is apparent that groundwater carbon concentrations are significantly lower than terrestrial (soil, sediment and river) concentrations. This indicates that terrestrial OM is biologically processed (and a potential source of inorganic carbon) or sorbed to mineral surfaces (a sink of carbon). This will be explored through an ARC Discovery research project which will investigate factors that determine groundwater organic matter concentration, how important is groundwater to the terrestrial carbon budget and under what conditions where groundwater is a carbon source or sink. This project is bringing together geochemists, ecologists, hydrologists and anyone with an interest in organic matter in groundwater. Specifically, the amount of colloid and dissolved organic matter present will be quantified, the rate and extent of biological processing, desorption and sorption will be investigated and the relative importance of each process to be determined. The processes that control organic matter in groundwater will be investigated at a range of field sites with differing surface soil, land cover, recharge type and hydrological properties. Preliminary results from various field sites has shown that sedimentary organic matter is mobilised as water flows through the hyporheic zone. The results from this project will provide guidelines for the management of groundwater resource as part of the carbon economy.
- ItemMolecular insights into the unique degradation trajectory of natural dissolved organic matter from surface to groundwater(Copernicus GmbH, 2021-04-19) McDonough, LK; Behnke, MI; Spencer, R; Marjo, CE; Andersen, MS; Meredith, KT; Rutlidge, H; Oudone, PP; O'Carroll, DM; McKenna, AM; Baker, AADissolved organic matter (DOM) comprises a large and complex range of molecules with varying mass, elemental arrangements, conformation, and polarity. These diverse molecules interact with the environment resulting in changes to their molecular character and reactivity over time. Significant advances in our understanding of the molecular character of reactive and recalcitrant DOM have been made throughout the past decade, largely due to the development of ultra-high resolution techniques such as Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). This understanding, however, is almost entirely based on surface water environments. Here, we investigate how the molecular properties of DOM change due to reactions occurring in a groundwater environment over time. We use FT-ICR MS combined with liquid chromatography organic carbon detection (LC-OCD), fluorescence and radiocarbon (14C) dissolved organic carbon (DOC) for a range of groundwater DOM samples, including the oldest DOC reported from a site which is not impacted by sedimentary organic carbon inputs (25,310 ± 600 years BP). Our results indicate that polarity and nominal oxidation state of carbon (NOSC) play a major role in the reactivity of groundwater DOM, with a preferential removal of hydrophilic, high oxygen to carbon (O/C) ratio molecules over time (rs = 0.91, p = 2.4 x 10-6). We also note an increase in likely bio-produced molecules containing low numbers of O atoms in deep methanogenic groundwater environments. These molecular formulae appear to accumulate due to the prolonged anoxic conditions which would not be experienced by surface water DOM. The decline in NOSC with increasing average bulk groundwater DOC age contrasts with findings from marine environments where NOSC has been reported to increase over time. Furthermore, the proportion of specific molecular formulae which are stable in marine waters, decline in groundwater as 14CDOC decreases (rs = 0.68, p = 6.9 x 10-3) suggesting that current indicators of DOM degradation state derived from marine environments are not applicable to groundwater environments. Our research shows that the molecular character of reactive DOM in groundwater differs from that of surface water due to exposure to different environments and processing mechanisms, suggesting that it is the interaction between external environmental factors and intrinsic DOM molecular properties which control DOM recalcitrance.
- ItemNatural organic matter in goundwater: carbon source or sink?(European Geosciences Union, 2019-04-07) Rutlidge, H; McDonough, LK; Oudone, PP; Andersen, MS; Baker, AA; Meredith, KT; O'Carroll, DM; Marjo, CE; Mustonen, OCarbon plays an essential role in all biological processes on the earth and hence it is important to Mustin the environment. The concentration of organic matter in groundwater, with a global median of 1.0 mg C/L, is often significantly lower than in adjacent soil and surface waters. The likely processes that are responsible for this decrease are sorption to mineral surfaces and biological processing by microbes as water travels through sediments. While these processes have been quantified individually at different sites, they have not been investigated concurrently, and hence the relative importance of each process is unknown. Therefore, the role of organic matter processes in groundwater and in the terrestrial global carbon budget is unknown. To investigate this a series of laboratory-based experiments were conducted, in conjunction with the organic matter characterization of field samples by Liquid Chromatography-Organic Carbon Detection (LC-OCD). LC-OCD is a size-exclusion based chromatography technique that separates dissolved organic carbon into five fractions based on their mass, plus a hydrophobic fraction, which remains in the column. For the laboratory-based experiments, the amount of sorption onto pure mineral surfaces (quartz sand, iron-coated sand, and calcium carbonate), desorption from natural sediments and biological degradation was investigated at a range of different locations in New South Wales, Australia. The sites covered a range of different aquifer materials (coastal sands, river alluvium and fractured meta-basalts), land cover and recharge type. At each site, groundwater samples were collected from wells located with varying distance from surface water bodies for the subsequent laboratory experiments. The results showed that predominately the humics fraction was adsorbing onto the mineral surfaces and the low-molecular weight neutrals were being biologically degraded. For the desorption experiments several fractions desorbed with the humics and hydrophobic fraction being dominant. The amount of desorption increased with increasing salinity and increasing number of cycles of drying and wetting. The LC-OCD results of field samples indicated that proportionally, sorption is more dominant than biological degradation. Hence changing environmental conditions, such as increasing salinity and/or drier conditions, could lead to a release of sorbed carbon.
- ItemThe new Chronos 14carbon-Cycle Facility, University of New South Wales, Sydney, Australia.(Australian Nuclear Science and Technology Organisation, 2021-11-17) Turney, CSM; Thomas, Z; Becerra-Valdivia, L; Palmer, JG; Haines, HA; Cadd, HR; Wacker, L; Baker, AA; Andersen, MS; Jacobsen, GE; Meredith, KT; Chinu, K; Hiscock, W; Vohra, J; Marjo, CEThe Chronos 14Carbon-Cycle Facility is a new radiocarbon laboratory at the University of New South Wales, Australia. Built around an Ionplus 200 kV MIni-CArbon DAting System (MICADAS) Accelerator Mass Spectrometer (AMS) installed in October 2019, the facility was established to address major challenges in the Earth, Environmental and Archaeological sciences. Here we report an overview of the Chronos facility, the pretreatment methods currently employed (bones, carbonates, peat, pollen, charcoal, and wood) and results of radiocarbon and stable isotope measurements undertaken on a wide range of sample types. Our measurements on international standards, known-age and blank samples demonstrate that the facility is capable of measuring 14C samples from the Anthropocene back to nearly 50,000 years ago. Future work will focus on improving our understanding of the Earth system and managing resources in a future warmer world.
- ItemA new conceptual framework for the transformation of groundwater dissolved organic matter(Springer Nature Limited, 2022-04-20) McDonough, LK; Andersen, MS; Behnke, MI; Rutlidge, H; Oudone, PP; Meredith, KT; O'Carroll, DM; Santos, IR; Marjo, CE; Spencer, RGM; McKenna, AM; Baker, AAGroundwater comprises 95% of the liquid fresh water on Earth and contains a diverse mix of dissolved organic matter (DOM) molecules which play a significant role in the global carbon cycle. Currently, the storage times and degradation pathways of groundwater DOM are unclear, preventing an accurate estimate of groundwater carbon sources and sinks for global carbon budgets. Here we reveal the transformations of DOM in aging groundwater using ultra-high resolution mass spectrometry combined with radiocarbon dating. Long-term anoxia and a lack of photodegradation leads to the removal of oxidised DOM and a build-up of both reduced photodegradable formulae and aerobically biolabile formulae with a strong microbial signal. This contrasts with the degradation pathway of DOM in oxic marine, river, and lake systems. Our findings suggest that processes such as groundwater extraction and subterranean groundwater discharge to oceans could result in up to 13 Tg of highly photolabile and aerobically biolabile groundwater dissolved organic carbon released to surface environments per year, where it can be rapidly degraded. These findings highlight the importance of considering groundwater DOM in global carbon budgets. © The Authors, Open Access under CC 4.0
- ItemA new conceptual framework for the transformation of groundwater dissolved organic matter(Springer Nature, 2022-04-20) McDonough, LK; Andersen, MS; Behnke, MI; Rutlidge, H; Oudone, PP; Meredith, KT; O'Carroll, DM; Santos, IR; Marjo, CE; Spencer, RGM; McKenna, AM; Baker, AAGroundwater comprises 95% of the liquid fresh water on Earth and contains a diverse mix of dissolved organic matter (DOM) molecules which play a significant role in the global carbon cycle. Currently, the storage times and degradation pathways of groundwater DOM are unclear, preventing an accurate estimate of groundwater carbon sources and sinks for global carbon budgets. Here we reveal the transformations of DOM in aging groundwater using ultra-high resolution mass spectrometry combined with radiocarbon dating. Long-term anoxia and a lack of photodegradation leads to the removal of oxidised DOM and a build-up of both reduced photodegradable formulae and aerobically biolabile formulae with a strong microbial signal. This contrasts with the degradation pathway of DOM in oxic marine, river, and lake systems. Our findings suggest that processes such as groundwater extraction and subterranean groundwater discharge to oceans could result in up to 13 Tg of highly photolabile and aerobically biolabile groundwater dissolved organic carbon released to surface environments per year, where it can be rapidly degraded. These findings highlight the importance of considering groundwater DOM in global carbon budgets. Crown Copyright © 2022
- ItemRadiocarbon protocols and first intercomparison results from the Chronos 14Carbon-Cycle Facility, University of New South Wales, Sydney, Australia(Cambridge University Press, 2021-05-11) Turney, CSM; Becerra-Valdivia, L; Sookdeo, A; Thomas, ZA; Palmer, JG; Haines, HA; Cadd, HR; Wacker, L; Baker, AA; Andersen, MS; Jacobsen, GE; Meredith, KT; Chinu, K; Bollhalder, S; Marjo, CEThe Chronos 14Carbon-Cycle Facility is a new radiocarbon laboratory at the University of New South Wales, Australia. Built around an Ionplus 200 kV MIni-CArbon DAting System (MICADAS) Accelerator Mass Spectrometer (AMS) installed in October 2019, the facility was established to address major challenges in the Earth, Environmental and Archaeological sciences. Here we report an overview of the Chronos facility, the pretreatment methods currently employed (bones, carbonates, peat, pollen, charcoal, and wood) and results of radiocarbon and stable isotope measurements undertaken on a wide range of sample types. Measurements on international standards, known-age and blank samples demonstrate the facility is capable of measuring 14C samples from the Anthropocene back to nearly 50,000 years ago. Future work will focus on improving our understanding of the Earth system and managing resources in a future warmer world. © The Author(s) 2021. Published by Cambridge University Press for the Arizona Board of Regents on behalf of the University of Arizona.
- ItemThe role of dissolved organic matter and groundwater biogeophysical processes in the carbon budget(National Centre for Groundwater Research And Training, 2017-07-11) Oudone, PP; Baker, AA; O'Carroll, DM; Andersen, MM; Rutlidge, H; McDonough, LL; Marjo, CE; Meredith, KTAtmospheric CO2 concentration is acknowledged to play an important role in climate change. However, quantifying more accurate predictions requires a sound understanding of the cycle and process of carbon especially in the environment. There has been extensive research on terrestrial carbon and the different conditions where it is a source or sink. However, the knowledge on whether groundwater organic matter is a carbon source or sink is limited. This work will explore the dynamic of groundwater organic matter including both its concentration and its rate and extent of biological processing and sorption. The UNSW Wellington Research Station was selected for groundwater sampling as it represents a fractured rock aquifer and alluvial aquifer for groundwater property and interaction investigation. Samples were collected from a transect of boreholes perpendicular from the river. Literature procedures were adopted for determining biological dissolved organic carbon and investigation of organic matter sorption on pure minerals (quartz sand, iron-coated quartz sand and calcium carbonate). For each sample collected total dissolved organic concentration was measured and the organic matter present was characterized by fluorescence spectroscopy and size-exclusion chromatographic technique, LC-OCD. There was greater sorption of organic matter with calcium carbonate, followed by iron-coated sand, while minimum sorption was observed with sand. This research in conjunction with similar studies in different environments will allow conclusions to be drawn groundwater organic matter and whether it is a carbon source or sink and thereby the findings can eventually have some policy application which will enable the management of the groundwater resources as part of the carbon economy.