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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. [ABSTRACT FROM AUTHOR]

Cathedral Cave, Wellington, Australia, is a natural laboratory for studying water movement and geochemical processes in the unsaturated zone by using artificial irrigation to activate drip sites within the cave. Water sampled from two drip sites activated by irrigations carried out in summer 2014 was analysed for dissolved inorganic ions and fluorescent organic matter. The analysis allowed the development of a conceptual flow path model for each drip site. DOM analysis was further complemented by liquid chromatography with organic carbon detection (LC-OCD), applied for the first time to karst drip waters, allowing the characterisation of six organic matter fractions. The differences in organic matter fractions at each drip site are interpreted as a signature of the proposed flow paths. LC-OCD was also compared with parallel factor analysis (PARAFAC) of the fluorescence and good correlations were observed for high molecular weight organic matter. Strong positive correlations were also observed for high molecular weight matter and Cu and Ni. This is suggestive of colloidal transport of Cu and Ni by organic matter with high molecular weight, while small molecular weight colloids were not efficient transporters. LC-OCD uniquely provides information on non-fluorescent organic matter and can be used to further quantify drip water organic matter composition. [ABSTRACT FROM AUTHOR]

Abstract: A 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. [Copyright &y& Elsevier]

• This work presents the largest dataset of groundwater DOC character using LC OCD. • The presence of sedimentary organic matter strongly influences the character of groundwater DOM. • High molecular weight DOM is processed out of groundwater as it moves through the subsurface. • The aquifer environment will influence the efficiency of different water treatments. 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 (LC OCD). 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. [ABSTRACT FROM AUTHOR]

Measurement of glycerol dialkyl glycerol tetraethers (GDGTs) preserved in speleothems offers a potential proxy for past temperature but, in general, their origin is unknown. To understand the source of speleothem GDGTs, we undertook an irrigation experiment to activate drip sites within a hydrogeochemically well characterised cave. The cave drip water was analysed for GDGTs, inorganic elements (major ions and trace elements), stable isotopes and dissolved organic matter concentration and character. Published speleothem GDGT records from the site have been observed to be dominated by isoprenoid GDGTs and interpreted as deriving from in situ microbial communities within the cave or vadose zone. The drip water in our irrigation experiment had a GDGT distribution distinct from that of soil and speleothem samples, providing direct evidence that the distinctive GDGT signature in speleothems is derived from a subsurface source. Analysis of GDGTs in this context allowed further elucidation of their source and transport in cave systems, enhancing our understanding of how they might be used as a temperature proxy. [ABSTRACT FROM AUTHOR]

Oxygen isotope ratios in speleothems may be affected by external processes that are independent of climate, such as karst hydrology and kinetic fractionation. Consequently, there has been a shift towards characterising and understanding these processes through cave monitoring studies, particularly focussing on temperate zones where precipitation exceeds evapotranspiration. Here, we investigate oxygen isotope systematics at Wellington Caves in semi-arid, SE Australia, where evapotranspiration exceeds precipitation. We use a novel D 2 O isotopic tracer in a series of artificial irrigations, supplemented by pre-irrigation data comprised four years of drip monitoring and three years of stable isotope analysis of both drip waters and rainfall. This study reveals that: (1) evaporative processes in the unsaturated zone dominate the isotopic composition of drip waters; (2) significant soil zone ‘wetting up’ is required to overcome soil moisture deficits in order to achieve infiltration, which is highly dependent on antecedent hydro-climatic conditions; (3) lateral flow, preferential flow and sorption in the soil zone are important in redistributing subsurface zone water; (4) isotopic breakthrough curves suggest clear evidence of piston-flow at some drip sites where an older front of water discharged prior to artificial irrigation water; and (5) water residence times in a shallow vadose zone (<2 m) are highly variable and can exceed six months. Oxygen isotope speleothem records from semi-arid regions are therefore more likely to contain archives of alternating paleo-aridity and paleo-recharge, rather than paleo-rainfall e.g. the amount effect or mean annual. Speleothem-forming drip waters will be dominated by evaporative enrichment, up to ∼3‰ in the context of this study, relative to precipitation-weighted mean annual rainfall. The oxygen isotope variability of such coeval records may further be influenced by flow path and storage in the unsaturated zone that is not only drip specific but also influenced by internal cave climatic conditions, which may vary spatially in the cave. [ABSTRACT FROM AUTHOR]

While several studies explore cave climate and thermal regimes, little is known about the controls on cave drip water temperature. Yet water temperature significantly influences biogeochemical processes associated with cave drips. To identify the processes that control the cave drip water temperature, we measured the temperatures at multiple locations along a speleothem flow path and drip sources (stalactites) concurrently with the drip rates in Cathedral Cave, Wellington, Australia. We monitored long-term drip water temperature, drip rates, surface and cave climate and in-cave evaporation rates and conducted 3 infiltration experiments with different flow, temperature and isotopic conditions. Our results show that the drip water temperature is controlled by multiple superimposed heat transport mechanisms that act upon the infiltrating water in the epikarst, the water film after it enters the cave and before it becomes a drip. The two main heat sources/sinks for drip water are the cave air and the surrounding rock. The subsurface temperature is coupled to the surface temperature by conduction through the soil and rock mass, but the cave climate is also coupled to the surface climate by venting. On a regional scale, drip temperatures are mainly driven by the annual ground surface temperature signal but damped with depth and shifted in time compared to the surface. On a local scale, the drip water temperature can differ significantly from cave air and speleothem temperature due to the latent heat exchange of evaporation and localised water film convection. The main controls are ground surface temperature, subsurface depth, air density induced ventilation, distance from entry and drip rate. We present a conceptual model that explains drip water temperature signals and provide signal driven guidance on best type and location for speleothem sampling. We anticipate that our results will significantly improve the understanding of temperature-dependent paleoclimate signals from speleothem archives. [ABSTRACT FROM AUTHOR]