Dioni I. Cendón

The use of environmental markers to distinguish marine vs. continental deposition and to quantify the significance of recycling in evaporite basins

Abstract Environmental markers, namely the bromine content of halite samples, the electrolyte content of primary fluid inclusions in halite and the isotopic composition of sulphates from two Tertiary evaporite sequences, provide complementary information on the depositional environment (marine vs. continental). The use of these markers, together with lithofacies and thicknesses of precipitated evaporites, enable the detection and quantification of evaporite recycling within evaporite basins. The information provided by the isolated use of each of these geochemical markers should be used with caution, as this could lead to erroneous interpretations of the depositional environment or may not detect significant evaporite recycling processes. The complementary information provided by geochemical markers enable quantification of solute input from recycling of previous precipitates within the basins themselves or from older evaporites. The input of recycled evaporites increases progressively, together with evaporite basin restriction to the open ocean.

The major-ion composition of Cenozoic seawater: The past 36 million years from fluid inclusions in marine halite

Fluid inclusions from ten Cenozoic (Eocene-Miocene) marine halites are used to quantify the major-ion composition (Mg2+, Ca2+, K+, Na+, SO42−, and Cl−) of seawater over the past 36 My. Criteria used to determine a seawater origin of the halites include: (1) stratigraphic, sedimentologic, and paleontologic observations; (2) Br− in halite; (3) δ34S of sulfate minerals; (4) 87Sr/86Sr of carbonates and sulfates; and (5) fluid inclusion brine compositions and evaporation paths, which must overlap from geographically separated basins of the same age to confirm a “global” seawater chemical signal. Changes in the major-ion chemistry of Cenozoic seawater record the end of a systematic, long term (>150 My) shift from the Ca2+-rich, Mg2+- and SO42−-poor seawater of the Mesozoic (“CaCl2 seas”) to the “MgSO4 seas” (with higher Mg2+ and SO42−>Ca2+) of the Cenozoic. The major ion composition of Cenozoic seawater is calculated for the Eocene-Oligocene (36-34 Ma), Serravallian-Tortonian (13.5-11.8 Ma) and the Messinian (6-5 Ma), assuming chlorinity (565 mmolal), salinity, and the K+ concentration (11 mmolal) are constant and the same as in modern seawater. Fluid inclusions from Cenozoic marine halites show that the concentrations of Mg2+and SO42− have increased in seawater over the past 36 My and the concentration of Ca2+ has decreased. Mg2+ concentrations increased from 36 mmolal in Eocene-Oligocene seawater (36-34 Ma) to 55 mmolal in modern seawater. The Mg2+/Ca2+ ratio of seawater has risen from ∼2.3 at the end of the Eocene, to 3.4 and 4.0, respectively, at 13.5 to 11.8 Ma and 6 to 5 Ma, and to 5 in modern seawater. Eocene-Oligocene seawater (36-34 Ma) has estimated ranges of SO42− = 14–23 mmolal and Ca2+ = 11–20 mmolal. If the (Ca2+)(SO42−) product is assumed to be the same as in modern seawater (∼300 mmolal2), Eocene-Oligocene seawater had Ca2+ ∼16 mmolal and SO42− ∼19 mmolal. The same estimates of Ca2+ and SO42− for Serravallian-Tortonian seawater (13.5-11.8 Ma) are SO42− = 19–27 mmolal and Ca2+ = 8–16 mmolal and SO42− ∼24 mmolal and Ca2+ ∼ 13 mmolal if the (Ca2+)(SO42−) product is equal to that in modern seawater. Messinian seawater has an estimated range of SO42− ∼21–29 mmolal and Ca2+ ∼7–15 mmolal with SO42− ∼26 mmolal and Ca2+ ∼12 mmolal assuming the (Ca2+)(SO42−) product is equal to that in modern seawater. Regardless of the estimation procedure, SO42− shows progressively increasing concentrations from 36 Ma to the present values, which are the highest of the Cenozoic.

Movement of a tritium plume in shallow groundwater at a legacy low-level radioactive waste disposal site in eastern Australia.

Between 1960 and 1968 low-level radioactive waste was buried in a series of shallow trenches near the Lucas Heights facility, south of Sydney, Australia. Groundwater monitoring carried out since the mid 1970s indicates that with the exception of tritium, no radioactivity above typical background levels has been detected outside the immediate vicinity of the trenches. The maximum tritium level detected in ground water was 390 kBq/L and the median value was 5400 Bq/L, decay corrected to the time of disposal. Since 1968, a plume of tritiated water has migrated from the disposal trenches and extends at least 100 m from the source area. Tritium in rainfall is negligible, however leachate from an adjacent and fill represents a significant additional tritium source. Study data indicate variation in concentration levels and plume distribution in response to wet and dry climatic periods and have been used to determine pathways for tritium migration through the subsurface.

Brine-mineral reactions in evaporite basins: Implications for the composition of ancient oceans

The chemical evolution of several European Mesozoic and Tertiary evaporite basins was reconstructed by using mineral associations, primary fluid-inclusion analyses, and numerical simulations of evaporation scenarios. The solute proportion recorded in the fluid inclusions can be explained by the evaporation of present-day seawater as a major recharge. The sulfate depletion in the brines is responsible for the type of potash deposit formed, potassium-magnessium sulfates or sylvite. This sulfate depletion can be due either to dolomitization or to the addition of a CaCl 2 -rich solution to the basin. The sulfate depletion occurred in varying intensity in basins of the same age, as well as throughout the evolution of the same basin. Therefore, changes in potash mineralogy and sulfate depletion in fluid inclusions are not conclusive arguments in favor of secular variations in the composition of the ocean, as recently proposed by several authors.

Groundwater residence time in a dissected and weathered sandstone plateau: Kulnura–Mangrove Mountain aquifer, NSW, Australia

Groundwater residence time in the Kulnura–Mangrove Mountain aquifer was assessed during a multi-year sampling programme using general hydrogeochemistry and isotopic tracers (H2O stable isotopes, δ13CDIC, 3H, 14C and 87Sr/86Sr). The study included whole-rock analysis from samples recovered during well construction at four sites to better characterise water–rock interactions. Based on hydrogeochemistry, isotopic tracers and mineral phase distribution from whole-rock XRD analysis, two main groundwater zones were differentiated (shallow and deep). The shallow zone contains oxidising Na–Cl-type waters, low pH, low SC and containing 3H and 14C activities consistent with modern groundwater and bomb pulse signatures (up to 116.9 pMC). In this shallow zone, the original Hawkesbury Sandstone has been deeply weathered, enhancing its storage capacity down to ∼50 m below ground surface in most areas and ∼90 m in the Peats Ridge area. The deeper groundwater zone was also relatively oxidised with a tendency towards Ca–HCO3-type waters, although with higher pH and SC, and no 3H and low 14C activities consistent with corrected residence times ranging from 11.8 to 0.9 ka BP. The original sandstone was found to be less weathered with depth, favouring the dissolution of dispersed carbonates and the transition from a semi-porous groundwater media flow in the shallow zone to fracture flow at depth, with both chemical and physical processes impacting on groundwater mean residence times. Detailed temporal and spatial sampling of groundwater revealed important inter-annual variations driven by groundwater extraction showing a progressive influx of modern groundwater found at >100 m in the Peats Ridge area. The progressive modernisation has exposed deeper parts of the aquifer to increased NO3− concentrations and evaporated irrigation waters. The change in chemistry of the groundwater, particularly the lowering of groundwater pH, has accelerated the dissolution of mineral phases that would generally be inactive within this sandstone aquifer triggering the mobilisation of elements such as aluminium in the aqueous phase.

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

Abstract 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 2H–18O 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 18O and 2H, 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.

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.

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 (δ13C-CH4), groundwater tritium (3H) and dissolved organic carbon (DOC) concentration. A continuous mobile CH4 survey adjacent to CSG developments was used to determine the source signature of CH4 derived from the WCM. Trends in groundwater δ13C-CH4 versus CH4 concentration, in association with DOC concentration and 3H analysis, identify locations where CH4 in the groundwater of the CRAA most likely originates from the WCM. The methodology is widely applicable in unconventional gas development regions worldwide for providing an early indicator of geological pathways of hydraulic connectivity.

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+240Pu in 0.45 μm-filtered water), and there is an associated contamination of Pu in surface soils. The highest 239+240Pu 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.

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 todays 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.