Naturally occurring radioactive materials in offshore infrastructure: Understanding formation and characteristics of baryte scale during decommissioning planning.

Contaminants, including naturally occurring radioactive material (NORM) of the 238-uranium and 232-thorium decay series, have been recognized as a global research priority to inform offshore petroleum infrastructure decommissioning decisions. This study aimed to characterize pipeline scale retrieved from a decommissioned subsea well tubular pipe through high-resolution elemental mapping and isotopic analysis. This was achieved by utilizing transmission electron microscopy, Synchrotron x-ray fluorescence, photostimulated luminescence autoradiography and Isotope Ratio Mass Spectrometry. The scale was identified as baryte (BaSO4) forming a dense crystalline matrix, with heterogenous texture and elongated crystals. The changing chemical and physical microenvironment within the pipe influenced the gradual growth rate of baryte over the production life of this infrastructure. A distinct compositional banding of baryte and celestine (SrSO4) bands was observed. Radioactivity attributed by the presence of radionuclides (226Ra, 228Ra) throughout the scale was strongly correlated with baryte. From the detailed scale characterization, we can infer the baryte scale gradually formed within the internals of the tubular well pipe along the duration of production (i.e., 17 years). This new knowledge and insight into the characteristics and formation of petroleum waste products will assist with decommissioning planning to mitigate potential radiological risks to marine ecosystems.

Rare earth elements and yttrium as tracers of waste/rock-groundwater interactions.

Increasing concentrations of Rare Earth Elements (REE) plus yttrium (REY) are entering the environment due to human activities. The similar chemical behaviour across the whole REY, i.e. the lanthanide series (lanthanum to lutetium) and yttrium, allows their use as tracers, fingerprinting rock-forming processes and fluid-rock interactions in earth science systems. However, their use in fingerprinting waste and particularly low-level radioactive waste has not received much attention, despite the direct use of REE in the nuclear industry and the traditional use of REE as proxies to understand the environmental mobility of the actinide series (actinium to lawrencium). The highly instrumented low-level radioactive waste site at Little Forest (Australia) allows a detailed REY study, investigating interactions with local strata, neighbouring waste forms and shallow groundwater flows. Groundwater samples and solids from cored materials were recovered from 2007 to 2012 from the study site and regional baseline sites in the same geological materials. The REY in water samples were analysed by automated chelation pre-concentration (SeaFast, ESI) followed by ICP-MS determination, while solid samples were analysed using Neutron Activation Analysis (NAA) and X-ray fluorescence scanning (ITRAX). Solid rocks showed no REY departed from typical Upper Crust compositions in either Little Forest or regional background sites. Shallow groundwater from ~4-5 m, at or slightly below waste trench levels, showed water-waste interaction as a marked enrichment, relative to shale-normalised patterns, in samarium, europium and gadolinium, with depleted yttrium. Leachate samples from the neighbouring urban landfill show different REY normalised patterns. REY distribution changes with depth through increased interaction with shales and sandstones. Variations in pH and redox conditions lead to widespread precipitation of Fe-hydroxides, which scavenge REY with differential uptake by precipitating solids, resulting in increases in Y and higher Y/Ho ratio in the groundwater along the flow path. Our study revealed that the Little Forest low-level radioactive waste has a REY fingerprint different to that of groundwater in surrounding land uses. REY can be used to fingerprint diverse waste sources, assess the mobility of lanthanides inferring the mobility of selected actinides, and to trace the fate of REY during groundwater recharge. The approach presented can refine source allocation and trace pollutant mobility in current and legacy urban, mixed and radioactive waste sites around the world.

Isotopic evidence for nitrate sources and controls on denitrification in groundwater beneath an irrigated agricultural district.

The application of N fertilisers to enhance crop yield is common throughout the world. Many crops have historically been, or are still, fertilised with N in excess of the crop requirements. A portion of the excess N is transported into underlying aquifers in the form of NO3-, which is potentially discharged to surface waters. Denitrification can reduce the severity of NO3- export from groundwater. We sought to understand the occurrence and hydrogeochemical controls on denitrification in NO3--rich aquifers beneath the Emerald Irrigation Area (EIA), Queensland, Australia, a region of extensive cotton and cereal production. Multiple stable isotope (in H2O, NO3-, DIC, DOC and SO42-) and radioactive isotope (3H and 36Cl) tracers were used to develop a conceptual N process model. Fertiliser-derived N is likely incorporated and retained in the soil organic N pool prior to its mineralisation, nitrification, and migration into aquifers. This process, alongside the near absence of other anthropogenic N sources, results in a homogenised groundwater NO3- isotopic signature that allows for denitrification trends to be distinguished. Regional-scale denitrification manifests as groundwater becomes increasingly anaerobic during flow from an upgradient basalt aquifer to a downgradient alluvial aquifer. Dilution and denitrification occurs in localised electron donor-rich suboxic hyporheic zones beneath leaking irrigation channels. Using approximated isotope enrichment factors, estimates of regional-scale NO3- removal ranges from 22 to 93% (average: 63%), and from 57 to 91% (average: 79%) beneath leaking irrigation channels. In the predominantly oxic upgradient basalt aquifer, raised groundwater tables create pathways for NO3- to be transported to adjacent surface waters. In the alluvial aquifer, the transfer of NO3- is limited both physically (through groundwater-surface water disconnection) and chemically (through denitrification). These observations underscore the need to understand regional- and local-scale hydrogeological processes when assessing the impacts of groundwater NO3- on adjacent and end of system ecosystems.

A 35 ka record of groundwater recharge in south-west Australia using stable water isotopes.

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.

Constraining source attribution of methane in an alluvial aquifer with multiple recharge pathways.

Identifying the source of methane (CH4) in groundwater is often complicated due to various production, degradation and migration pathways, particularly in settings where there are multiple groundwater recharge pathways. This study demonstrates the ability to constrain the origin of CH4 within an alluvial aquifer that could be sourced from in situ microbiological production or underlying formations at depth. To characterise the hydrochemical and microbiological processes active within the alluvium, previously reported hydrochemical data (major ion chemistry and isotopic tracers (3H, 14C, 36Cl)) were interpreted in the context of CH4 and carbon dioxide (CO2) isotopic chemistry, and the microbial community composition in the groundwater. The rate of observed oxidation of CH4 within the aquifer was then characterised using a Rayleigh fractionation model. The stratification of the hydrochemical facies and microbiological community populations is interpreted to be a result of the gradational mixing of water from river leakage and floodwater recharge with water from basal artesian inflow. Within the aquifer there is a low abundance of methanogenic archaea indicating that there is limited biological potential for microbial CH4 production. Our results show that the resulting interconnection between hydrochemistry and microbial community composition affects the occurrence and oxidation of CH4 within the alluvial aquifer, constraining the source of CH4 in the groundwater to the geological formations beneath the alluvium.

Radionuclide distributions and migration pathways at a legacy trench disposal site.

This paper examines the distributions of several anthropogenic radionuclides (239+240Pu, 241Am, 137Cs, 90Sr, 60Co and 3H) at a legacy trench disposal site in eastern Australia. We compare the results to previously published data for Pu and tritium at the site. Plutonium has previously been shown to reach the surface by a bath-tubbing mechanism, following filling of the former trenches with water during intense rainfall events. This has led to some movement of Pu away from the trenched area, and we also provide evidence of elevated Pu concentrations in shallow subsurface layers above the trenched area. The distribution of 241Am is similar to Pu, and this is attributed to the similar chemistry of these actinides and the likely in-situ generation of 241Am from its parent 241Pu. Concentrations of 137Cs are mostly low in surface soils immediately above the trenches. However, similar to the actinides, there is evidence of elevated 137Cs and 90Sr concentrations in shallow subsurface layers above the trenched area. While the subsurface radionuclide peaks suggest a mechanism of subsurface transport, their interpretation is complicated by the presence of soil layers added following disposals and during the subsequent years. The distribution of 90Sr and 137Cs at the ground surface shows some elevated levels immediately above the trenches which were filled during the final 24 months of disposal operations. This is in agreement with disposal records, which indicate that greater amounts of fission products were disposed in this period. The surface distribution of 239+240Pu is also consistent with the disposal documents. Although there is extensive evidence of a mobile tritium plume in groundwater, migration of the other radionuclides by this pathway is limited. The data highlight the importance of taking into account multiple pathways for the mobilisation of key radioactive contaminants at legacy waste trench sites.

Rainfall isotope variations over the Australian continent - Implications for hydrology and isoscape applications.

This paper presents a continental scale interpretation of δ2H and δ18O in Australian precipitation, incorporating historical GNIP data at seven sites (1962-2002) and 8-12 years of new monthly data from 15 sites from 2003 to 2014. The more than doubling of stations and the significant time series duration allow for an improved analysis of Australian precipitation isotopes. Local meteoric water lines were developed for each site, and for the Australian continent. When the annual precipitation weighted values were used, the Australian meteoric water line was δ2H = 8.3 δ18O + 14.1‰. Precipitation amount was found to be a stronger driver of precipitation isotopes than temperature at most sites, particularly those affected by tropical cyclones and the monsoon. Latitude, elevation and distance from the coast were found to be stronger drivers of spatial variability than temperature or rainfall amount. Annual isoscapes of δ2H, δ18O and deuterium excess were developed, providing an improved tool to estimate precipitation isotope inputs to hydrological systems. Because of the complex climate, weather and oceanic moisture sources affecting Australia, regional groupings were used instead of the climate zone approach and additional data was included to improve the coverage in data poor regions. Regression equations for the isoscape were derived using latitude, altitude and distance from the coast as predictor variables. We demonstrate how this isoscape can be used as a tool for interpreting groundwater recharge processes using examples from across Queensland and New South Wales, including the Murray Darling Basin. Groundwater isotopes at sites where direct local recharge occurs are similar to rainfall, but for inland sites, which are often arid or semi-arid, a disconnect between shallow groundwater and local rainfall is observed; the departure in deuterium excess for these sites increases with aridity and distance from the headwaters where flooding originates.

Geochemical indicators of the origins and evolution of methane in groundwater: Gippsland Basin, Australia.

Recent expansion of shale and coal seam gas production worldwide has increased the need for geochemical studies in aquifers near gas deposits, to determine processes impacting groundwater quality and better understand the origins and behavior of dissolved hydrocarbons. We determined dissolved methane concentrations (n = 36) and δ13C and δ2H values (n = 31) in methane and groundwater from the 46,000-km2 Gippsland Basin in southeast Australia. The basin contains important water supply aquifers and is a potential target for future unconventional gas development. Dissolved methane concentrations ranged from 0.0035 to 30 mg/L (median = 8.3 mg/L) and were significantly higher in the deep Lower Tertiary Aquifer (median = 19 mg/L) than the shallower Upper Tertiary Aquifer (median = 3.45 mg/L). Groundwater δ13CDIC values ranged from -26.4 to -0.4 ‰ and were generally higher in groundwater with high methane concentrations (mean δ13CDIC = -9.5 ‰ for samples with >3 mg/L CH4 vs. -16.2 ‰ in all others), which is consistent with bacterial methanogenesis. Methane had δ13CCH4 values of -97.5 to -31.8 ‰ and δ2HCH4 values of -391 to -204 ‰ that were also consistent with bacterial methane, excluding one site with δ13CCH4 values of -31.8 to -37.9 ‰, where methane may have been thermogenic. Methane from different regions and aquifers had distinctive stable isotope values, indicating differences in the substrate and/or methanogenesis mechanism. Methane in the Upper Tertiary Aquifer in Central Gippsland had lower δ13CCH4 (-83.7 to -97.5 ‰) and δ2HCH4 (-236 to -391 ‰) values than in the deeper Lower Tertiary Aquifer (δ13CCH4 = -45.8 to -66.2 ‰ and δ2HCH4 = -204 to -311 ‰). The particularly low δ13CCH4 values in the former group may indicate methanogenesis at least partly through carbonate reduction. In deeper groundwater, isotopic values were more consistent with acetate fermentation. Not all methane at a given depth and location is interpreted as being necessarily produced in situ. We propose that high dissolved sulphate concentrations in combination with high methane concentrations can indicate gas resulting from contamination and/or rapid migration as opposed to in situ bacterial production or long-term migration. Isotopes of methane and dissolved inorganic carbon (DIC) serve as further lines of evidence to distinguish methane sources. The study demonstrates the value of isotopic characterisation of groundwater including dissolved gases in basins containing hydrocarbons.

Using 3D geological modelling and geochemical mixing models to characterise alluvial aquifer recharge sources in the upper Condamine River catchment, Queensland, Australia.

The influence of mountain front recharge on the water balance of alluvial valley aquifers located in upland catchments of the Condamine River basin in Queensland, Australia, is investigated through the development of an integrated hydrogeological framework. A combination of three-dimensional (3D) geological modelling, hydraulic gradient maps, multivariate statistical analyses and hydrochemical mixing calculations is proposed for the identification of hydrochemical end-members and quantification of the relative contributions of each end-member to alluvial aquifer recharge. The recognised end-members correspond to diffuse recharge and lateral groundwater inflows from three hydrostratigraphic units directly connected to the alluvial aquifer. This approach allows mapping zones of potential inter-aquifer connectivity and areas of groundwater mixing between underlying units and the alluvium. Mixing calculations using samples collected under baseflow conditions reveal that lateral contribution from a regional volcanic aquifer system represents the majority (41%) of inflows to the alluvial aquifer. Diffuse recharge contribution (35%) and inflow from two sedimentary bedrock hydrostratigraphic units (collectively 24%) comprise the remainder of major recharge sources. A detailed geochemical assessment of alluvial groundwater evolution along a selected flowpath of a representative subcatchment of the Condamine River basin confirms mixing as a key process responsible for observed spatial variations in hydrochemistry. Dissolution of basalt-related minerals and dolomite, CO2 uptake, ion-exchange, precipitation of clay minerals, and evapotranspiration further contribute to the hydrochemical evolution of groundwater in the upland alluvial aquifer. This study highlights the benefits of undertaking an integrated approach that combines multiple independent lines of evidence. The proposed methods can be applied to investigate processes associated with inter-aquifer mixing, including groundwater contamination resulting from depressurisation of underlying geological units hydraulically connected to the shallower water reservoirs.

Origin of high ammonium, arsenic and boron concentrations in the proximity of a mine: Natural vs. anthropogenic processes.

High ammonium (NH4), arsenic (As) and boron (B) concentrations are found in aquifers worldwide and are often related to human activities. However, natural processes can also lead to groundwater quality problems. High NH4, As and B concentrations have been identified in the confined, deep portion of the Niebla-Posadas aquifer, which is near the Cobre Las Cruces (CLC) mining complex. The mine has implemented a Drainage and Reinjection System comprising two rings of wells around the open pit mine, were the internal ring drains and the external ring is used for water reinjection into the aquifer. Differentiating geogenic and anthropogenic sources and processes is therefore crucial to ensuring good management of groundwater in this sensitive area where groundwater is extensively used for agriculture, industry, mining and human supply. No NH4, As and B are found in the recharge area, but their concentrations increase with depth, salinity and residence time of water in the aquifer. The increased salinity down-flow is interpreted as the result of natural mixing between infiltrated meteoric water and the remains of connate waters (up to 8%) trapped within the pores. Ammonium and boron are interpreted as the result of marine solid organic matter degradation by the sulfate dissolved in the recharge water. The light δ(15)NNH4 values confirm that its origin is linked to marine organic matter. High arsenic concentrations in groundwater are interpreted as being derived from reductive dissolution of As-bearing goethite by dissolved organic matter. The lack of correlation between dissolved Fe and As is explained by the massive precipitation of siderite, which is abundantly found in the mineralization. Therefore, the presence of high arsenic, ammonium and boron concentrations is attributed to natural processes. Ammonium, arsenic, boron and salinity define three zones of groundwater quality: the first zone is close to the recharge area and contains water of sufficient quality for human drinking; the second zone is downflow and contains groundwater suitable for continuous irrigation but not drinkable due to high ammonium concentrations; and the third zone contains groundwater of elevated salinity (up to 5940 µS cm(-1)) and is not useable due to high ammonium, arsenic and boron concentrations.

Marine water from mid-Holocene sea level highstand trapped in a coastal aquifer: Evidence from groundwater isotopes, and environmental significance.

A multi-layered coastal aquifer in southeast Australia was assessed using environmental isotopes, to identify the origins of salinity and its links to palaeo-environmental setting. Spatial distribution of groundwater salinity (electrical conductivity values ranging from 0.395 to 56.1 mS/cm) was examined along the coastline along with geological, isotopic and chemical data. This allowed assessment of different salinity sources and emplacement mechanisms. Molar chloride/bromide ratios range from 619 to 1070 (621 to 705 in samples with EC >15 mS/cm), indicating salts are predominantly marine. Two distinct vertical salinity profiles were observed, one with increasing salinity with depth and another with saline shallow water overlying fresh groundwater. The saline shallow groundwater (EC=45.4 to 55.7 mS/cm) has somewhat marine-like stable isotope ratios (δ(18)O=-2.4 to -1.9 ‰) and radiocarbon activities indicative of middle Holocene emplacement (47.4 to 60.4pMC). This overlies fresher groundwater with late Pleistocene radiocarbon ages and meteoric stable isotopes (δ(18)O=-5.5 to -4.6‰). The configuration suggests surface inundation of the upper sediments by marine water during the mid-Holocene (c. 2-8 kyr BP), when sea level was 1-2m above today's level. Profiles of chloride, stable isotopes, and radiocarbon indicate mixing between this pre-modern marine water and fresh meteoric groundwater to varying degrees around the coastline. Mixing calculations using chloride and stable isotopes show that in addition to fresh-marine water mixing, some salinity is derived from transpiration by halophytic vegetation (e.g. mangroves). The δ(13)C ratios in saline water (-17.6 to -18.4‰) also have vegetation/organic matter signatures, consistent with emplacement by surface inundation and extensive interaction between vegetation and recharging groundwater. Saline shallow groundwater is preserved only in areas where low permeability sediments have slowed subsequent downwards propagation. The configuration is unlikely to be stable long-term due to fluid density; this may be exacerbated by pumping the underlying aquifer.

Assessing Connectivity Between an Overlying Aquifer and a Coal Seam Gas Resource Using Methane Isotopes, Dissolved Organic Carbon and Tritium.

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 (δ(13)C-CH4), groundwater tritium ((3)H) 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 δ(13)C-CH4 versus CH4 concentration, in association with DOC concentration and (3)H 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.

Trench 'bathtubbing' and surface plutonium contamination at a legacy radioactive waste site.

Radioactive waste containing a few grams of plutonium (Pu) was disposed between 1960 and 1968 in trenches at the Little Forest Burial Ground (LFBG), near Sydney, Australia. A water sampling point installed in a former trench has enabled the radionuclide content of trench water and the response of the water level to rainfall to be studied. The trench water contains readily measurable Pu activity (~12 Bq/L of (239+240)Pu in 0.45 µm-filtered water), and there is an associated contamination of Pu in surface soils. The highest (239+240)Pu soil activity was 829 Bq/kg in a shallow sample (0-1 cm depth) near the trench sampling point. Away from the trenches, the elevated concentrations of Pu in surface soils extend for tens of meters down-slope. The broader contamination may be partly attributable to dispersion events in the first decade after disposal, after which a layer of soil was added above the trenched area. Since this time, further Pu contamination has occurred near the trench-sampler within this added layer. The water level in the trench-sampler responds quickly to rainfall and intermittently reaches the surface, hence the Pu dispersion is attributed to saturation and overflow of the trenches during extreme rainfall events, referred to as the 'bathtub' effect.

Using 14C and 3H to delineate a recharge 'window' into the Perth Basin aquifers, North Gnangara groundwater system, Western Australia.

The Gnangara Mound and the underlying Perth Basin aquifers are the largest source of groundwater for the southwest of Australia, supplying between 35 and 50% of Perth's potable water (2009-2010). However, declining health of wetlands on the Mound coupled with the reduction in groundwater levels from increased irrigation demands and drier climatic conditions means this resource is experiencing increased pressures. The northern Gnangara is an area where the Yarragadee aquifer occurs at shallow depths (~50 m) and is in direct contact with the superficial aquifer, suggesting the possibility of direct recharge into a generally confined aquifer. Environmental isotopes ((14)C and (3)H) and hydrochemical modelling were used to assess the presence of a recharge 'window' as well as understand the groundwater residence time within different aquifers. Forty-nine groundwater samples were collected from depths ranging from 11 to 311 m below ground surface. The isotopic variation observed in the superficial aquifer was found to be controlled by the different lithologies present, i.e. quartz-rich Bassendean Sand and carbonate-rich sediments of the Ascot Formation. Rainfall recharge into the Bassendean Sand inherits its dissolved inorganic carbon from the soil CO(2). Organic matter throughout the soil profile is degraded by oxidation leading to anoxic/acidic groundwater, which if in contact with the Ascot Formation leads to enhanced dissolution of carbonates. Hydrochemical mass balance modelling showed that carbonate dissolution could contribute 1-2 mmol kg(-1) of carbon to groundwaters recharged through the Ascot Formation. The corrected groundwater residence times of the Yarragadee aquifer in the northern part of the study area ranged from 23 to 35 ka, while waters in the southeastern corner ranged from sub-modern to 2 ka. Groundwater ages increase with distance radiating from the recharge 'window'. This study delineates a recharge 'window' into the commonly presumed confined aquifers of the Perth Basin, highlighting the need for appropriate sustainable management.

Evaporative isotope enrichment as a constraint on reach water balance along a dryland river.

Deuterium and oxygen-18 enrichment in river water during its transit across dryland region is found to occur systematically along evaporation lines with slopes of close to 4 in (2)H-(18)O space, largely consistent with trends predicted by the Craig-Gordon model for an open-water dominated evaporating system. This, in combination with reach balance assessments and derived runoff ratios, strongly suggests that the enrichment signal and its variability in the Barwon-Darling river, Southeastern Australia is acquired during the process of evaporation from the river channel itself, as enhanced by the presence of abundant weirs, dams and other storages, rather than reflecting inherited enrichment signals from soil water evaporation in the watershed. Using a steady-state isotope mass balance analysis based on monthly (18)O and (2)H, we use the isotopic evolution of river water to re-construct a perspective of net exchange between the river and its contributing area along eight reaches of the river during a drought period from July 2002 to December 2003, including the duration of a minor flow event. The resulting scenario, which uses a combination of climatological averages and available real-time meteorological data, should be viewed as a preliminary test of the application rather than as a definitive inventory of reach water balance. As expected for a flood-driven dryland system, considerable temporal variability in exchange is predicted. While requiring additional real-time isotopic data for operational use, the method demonstrates potential as a non-invasive tool for detecting and quantifying water diversions, one that can be easily incorporated within existing water quality monitoring activities.