Thin section, XRD, SEM, and isotopic techniques have been used to study authigenic kaolinite occurring in reservoir sandstones of the Lower Permian Aldebaran Sandstone. Where the unit is no longer an active aquifer, kaolinite is an intermediate-stage phase, and is highly depleted in deuterium (δDSMOW = −115 to −99‰) and 18O (δ18OSMOW = +7.8 to +8.9‰), indicating that precipitation must have been from meteoric water. Deep penetration of this water is linked to Late Triassic deformation and uplift of the Denison Trough sequence, an event which led to exposure of the Aldebaran Sandstone by the Early Jurassic prior to its re-burial beneath Jurassic and Cretaceous sedimentary rocks. The same water was probably involved in the creation of secondary porosity in the interval.

Where the Aldebaran Sandstone is presently undergoing meteoric flushing, kaolinite is relatively enriched in deuterium (δDSMOW = −104 to −93‰) and 18O (δ18OSMOW = +11.7 to +14.6‰), reflecting precipitation largely from post-Mesozoic meteoric water which was isotopically heavier than the Mesozoic water involved in intermediate-stage kaolinite precipitation. This temporal shift in meteoric water isotopic composition is related to the northward drift of the Australian continent to lower latitudes since the Mesozoic Era.

When present at elevated levels in drinking water, arsenic is toxic, and magnesian clays are gaining recognition as a source of elevated arsenic in groundwater. In the crust and upper mantle of Earth, arsenic incorporation into clay minerals is influenced by geochemical conditions associated with hydrothermal fluids and metamorphic processes (e.g. serpentinization), meaning that As is a useful tracer of fluid-flow in the deep Earth. To improve understanding of arsenic speciation in groundwater, sediments, soils, and hydrothermal-metamorphic systems, the present study examined arsenic incorporation into magnesian clays by synthesis of serpentine minerals (200oC, 10 d) with varied concentrations of Si, Al, As5+, and As3+. The synthesis experiments produced two distinct crystal types, tubular and platy serpentines, each with 10–15% randomly interstratified talc layers. X-ray absorption spectroscopy indicated that As5+ and As3+ occurred in the tetrahedral sheet. Single-crystal analysis revealed that tubular crystals contained up to 1 wt.% arsenic [Mg2.8(Si1.8As0.2)O5(OH)4] (mean 0.2 wt.% As). The mean composition of platy, high-Al crystals is (Mg1.8Al0.7)(Si2.0)O5(OH)4, and that of platy, medium-Al crystals with As3+ is (Mg2.07Al0.52) (Si1.97As3+0.03)O5(OH)4. Charge, geometry, and radius of tetrahedral AsO43– oxyanions are similar to tetrahedral SiO44–, and this facilitates fixation of As5+ into the tetrahedral sheet of clay minerals. The geometry and size of the larger As3+ in tetrahedral sites (as a pyramidal AsO33– oxyanion) may limit incorporation relative to As5+. Arsenic-bearing Mg clays crystallize in alkaline environments where AsO43– or AsO33– are the dominant As species and where high pH accompanies crystallization of serpentine, talc, chlorite, or Mg-smectite. The presence of tetrahedral As in these clays raises the possibility of tetrahedral As in other Mg clays (e.g. sepiolite or kerolite) as well.

The Netherlands has ample geothermal resources. During the last decade, development of these resources has picked up fast. In 2007 one geothermal system had been realised; to date (1 January 2019), 24 have been. Total geothermal heat production in 2018 was 3.7 PJ from 18 geothermal systems. The geothermal sources are located in the same reservoirs/aquifers in which the oil and gas accumulations are hosted: Cenozoic, Upper Jurassic – Lower Cretaceous, Triassic and Rotliegend reservoirs. Additionally, the yet unproven hydrocarbon play in the Lower Carboniferous (Dinantian) Limestones delivered geothermal heat in two geothermal systems. This is in contrast to the Upper Cretaceous and Upper Carboniferous with no producing geothermal systems but producing hydrocarbon fields. Similar to hydrocarbon development, developing the geothermal source relies on fluid flow through the reservoir. For geothermal application a transmissivity of 10 Dm is presently thought to be a minimum value for a standard doublet system. Regional mapping of the geothermal plays, with subsequent resource mapping, by TNO discloses the areas with favourable transmissivity within play areas for geothermal development. The website www.ThermoGis.nl provides the tool to evaluate the geothermal plays on a sub-regional scale. The Dutch geothermal source and resource portfolio can be classified using geothermal play classification of, for example, Moeck (2014). An appropriate adjective for play classification for the Dutch situation would be the predominant permeability type: matrix, karst, fracture or fault permeability. The Dutch geothermal play is a matrix-permeability dominated ‘Hot Sedimentary Aquifer’, ‘Hydrothermal’ or ‘Intra-cratonic Conductive’ play. The Dutch ‘Hot Sedimentary Aquifer’ play is subdivided according to the lithostratigraphical annotation of the reservoir. The main geothermal plays are the Delft Sandstone and Slochteren Sandstone plays.

The radioactive contaminant plume in groundwater at the Karachai Lake site has been examined further. The source of pollution is the Karachai Lake which was used as a reservoir for liquid radioactive waste (LRW) from the Radiochemical Production Association “Mayak” (South Urals, Russia). Taking into account that colloid-facilitated transport of radionuclides can substantially increase the contaminant migration velocity, the composition and structure of colloid particles from the groundwater within the contaminant plume were studied. Sampling of groundwater was carried out in the observation well within the contaminant plume. Different fractions of colloid particles were extracted from the groundwater samples by sequential filtration through membranes with decreasing pore size. Chemical and mineralogical compositions of the colloid particles were determined by X-ray photoelectron spectroscopy in combination with ion etching of the particle surfaces. The host rocks were studied using characteristic samples from the surface outcrop nearest to the observation well. The analysis showed that the colloid particles consisted of an inorganic core with a discontinuous organic cover. The inorganic core was close in composition to the host rocks along the flow path with a predominance of layered hydrosilicates.

Degradation of contaminant hydrocarbons in groundwater by microbially mediated oxidation, linked to the reduction of electron acceptors, is fundamental to the strategy of ‘monitored natural attenuation’ (MNA) for oxidizable hydrocarbons, which is increasingly being adopted at polluted aquifer sites throughout Europe and North America. Commonly, oxygen is depleted and following the reduction of nitrate, solid-phase Fe oxides become the dominant electron acceptors. Arsenic, associated with Fe and Mn oxides in soils and sediments, may therefore be mobilized to groundwater and pose an additional threat to environmental receptors. In a pilot study of three aquifers in England, we have examined the extent to which arsenic is released to groundwater under Fe(III)-reducing conditions imposed by contaminant hydrocarbons. Results show that arsenic is locally mobilized in the Chalk to <10 μg/1, in Quaternary gravels to 70 μg/1 and in the Triassic sandstones to 160 μg/1. At the Chalk and Quaternary gravels sites arsenic mobilization is demonstrably linked to reduction of Fe- and Mn-oxides. This is not so at the Triassic sandstone site, where release of arsenic is related to elevated bicarbonate alkalinity. Redox-driven arsenic mobilization at other Triassic sandstone locations is possible. Further work is required on the solid-phase sources of arsenic in the aquifers, and to relate the hydrochemical observations to groundwater hydraulic conditions.

Arsenic mobilization and Fe(III) reduction in acetate-amended sediments collected from a range of depths from an aquifer with elevated groundwater arsenic concentrations in West Bengal were monitored over a 1 month period. Significant arsenic release was noted in sediment collected from 24 m and 45 m depth, with some Fe(III) reduction also observed in the 24 m sample. The structure of the microbial communities present in the sediments prior to incubation showed marked differences down the sediment column. Profiling of the microbial community in the 24 m and 45 m samples revealed a relatively complex make-up, with Acinetobacter species comprising the bulk of the 24 m sedimentary bacterial population, but no previously characterized As(V)-reducers were detected in either sample.

Determination of the solid-phase arsenic speciation in sediments hosting high-arsenic groundwaters, utilized for drinking and irrigation in Bengal, SE Asia and elsewhere is important in order to understand the biogeochemistry of arsenic. Despite this, there is a relative paucity of speciation data for solid-phase arsenic in such systems, due to preservation difficulties, low arsenic concentrations in the sediments, multiple coordination environments and sample heterogeneity. In this study, X-ray absorption near edge structure spectroscopy was used in conjunction with linear least-squares fitting of model compounds to determine the oxidation state of arsenic in sediments from West Bengal and Cambodia. Whatever the collection and storage method used, substantial oxidation of arsenic was commonly observed over periods of weeks to several months. Sands were particularly susceptible to changes in arsenic oxidation state during storage. Analysis within two or three weeks of collection is therefore recommended, whilst on-site storage under a nitrogen atmosphere immediately after collection is particularly recommended for the preservation of sandy samples. Both muds and sands from West Bengal and Cambodia were dominated by arsenite (As(III)) with <35±10% arsenate (As(V)). Complete oxidation to arsenate was never observed suggesting that a significant proportion of the sedimentary arsenic is inaccessible within crystalline phases. Centrifuging under anaerobic conditions enabled more detailed information about a variety of arsenic coordination environments to be determined.

Arsenic and fluoride in groundwater from Quaternary loess deposits in Argentina pose major health concerns. Common sources for arsenic and fluoride have been suggested but the processes of mobilization are disputed, and distributions in groundwater are largely unresolved at a sample density >1/50 km2. At Los Pereyras in Tucumán Province, northern Argentina, we have evaluated distributions and hydrochemical associations of arsenic and fluoride with a sample density of 0.75 per km2 over an area of 75 km2, to a depth of 230 m. Groundwater in the loess is oxic and alkaline. Fluoride is restricted to the upper 20 m of the Quaternary loess, where it reaches 8.3 mg/1. Arsenic has a vertical layering consistent with that of fluoride, ranging from 20 to 760 μg/1 in the upper 20 m and 58—163 μg/l below this. There are two sources of arsenic, one unrelated to the fluoride source. Positive correlations between arsenic and fluoride with pH, but not with alkalinity, support desorption from iron oxyhydroxides as the likely mechanism of release to groundwater for arsenic and fluoride, rather than the weathering of silicate minerals. Stratigraphic and/or palaeohydrological controls may explain the observed depth distributions within the loess aquifer.

We conducted an isotopic analysis of groundwater in Orange County, California, USA, around the Talbert Seawater Injection Barrier to determine if recycled water, used to artificially recharge local aquifers, carries a unique isotopic signature that can be used as a tracer. From September 2014 to April 2015, we collected groundwater from six privately owned wells within the coastal groundwater basin, along with various surface waters. All water samples were analyzed for their stable isotopic composition (δ18O, δD), the δ13C and 14C signature of the dissolved inorganic carbon (DIC) pool, DIC concentration, pH, and salinity. The DIC of groundwater mixing with recycled water is enriched in 14C above natural background levels, with varying signal strength through time, depleted in δ13C, and low in DIC concentration. Water isotopes further suggest that recycled water is a mixture of Colorado River water and regional groundwater. In contrast, groundwater found further away from the injection barrier has carbon and water isotope composition consistent with regional groundwater and Santa Ana River water. Our findings imply that recycled water injected through the Talbert Barrier is isotopically unique, and that 14C enrichment may be used as an intrinsic tracer of artificial recharge within the basin.

The risk of five pesticides (atrazine, simazine, bentazone, mecoprop and MCPA) contaminating a Quaternary phreatic aquifer (the water supply area of Sint-Jansteen, the Netherlands) is assessed based on laboratory experiments and solute transport modelling (MODFLOW-MT3D). Batch experiments either show long half-lives (at least 1500 days) or no degradation at all for bentazone, atrazine and simazine while mecoprop and especially MCPA degrade much faster (half-lives down to 4.1 days). Column experiments show significant sorption to the aquifer sediment only for atrazine and simazine under certain circumstances. A series of experiments were conducted during which the type of the sediment, the grain size, the content of the organic matter and the acidity of the groundwater were varied. These experimental results were subsequently incorporated in a solute transport model for the aquifer resulting in the following ranking of the contamination risk for the selected pesticides (from low to high): MCPA, mecoprop, simazine, atrazine, bentazone. This ranking was confirmed by observed pesticide concentrations in samples taken from piezometers and extraction wells from the aquifer.

In this paper we present a probabilistic fast model for performance assessment of geothermal doublets for direct heat applications. It is a simple yet versatile and multipurpose tool. It can be well applied in better understanding the sensitivity of performance to key subsurface parameters and depth trends therein, and for assessing the probability of success for geothermal projects under technical and financial constraints.

The underlying algorithms deliver a sensible accuracy given the uncertainties associated with geothermal projects at exploration state. A public release of the software, available under the name of DoubletCalc, is easy to handle and requires a limited set of input parameters. Thanks to an open source code, DoubletCalc can be implemented in other software applications and extended as it has been implemented for the integration into the national geothermal information system in the Netherlands (ThermoGIS, 2011).

Apart from its application for site assessments, the tool can be integrated into automated workflows processing faster representations of key aquifer properties and capable to produce indicative maps for predicted doublet power, economic feasibility and prediction of cumulative amount of heat that can be recovered. These capabilities are specifically important for decision support for policymakers while assessing the effects of particular insurance schemes and funding mechanisms.

DoubletCalc cannot and is not intended to substitute geologic exploration approaches. As exploration measures, such as seismic surveys are cost intensive, DoubletCalc can be used to focus geothermal exploration on areas and sites where an enhanced probability of success can be expected.