Using 14C and 3H to understand groundwater flow and recharge in an aquifer window

Knowledge of groundwater residence times and recharge locations is vital to the sustainable management of groundwater resources. Here we investigate groundwater residence times and patterns of recharge in the Gellibrand Valley, southeast Australia, where outcropping aquifer sediments of the Eastern View Formation form an "aquifer window" that may receive diffuse recharge from rainfall and recharge from the Gellibrand River. To determine recharge patterns and groundwater flow paths, environmental isotopes (3H, 14C, δ13C, δ18O, δ2H) are used in conjunction with groundwater geochemistry and continuous monitoring of groundwater elevation and electrical conductivity. The water table fluctuates by 0.9 to 3.7 m annually, implying recharge rates of 90 and 372 mm yr−1. However, residence times of shallow (11 to 29 m) groundwater determined by 14C are between 100 and 10 000 years, 3H activities are negligible in most of the groundwater, and groundwater electrical conductivity remains constant over the period of study. Deeper groundwater with older 14C ages has lower δ18O values than younger, shallower groundwater, which is consistent with it being derived from greater altitudes. The combined geochemistry data indicate that local recharge from precipitation within the valley occurs through the aquifer window, however much of the groundwater in the Gellibrand Valley predominantly originates from the regional recharge zone, the Barongarook High. The Gellibrand Valley is a regional discharge zone with upward head gradients that limits local recharge to the upper 10 m of the aquifer. Additionally, the groundwater head gradients adjacent to the Gellibrand River are generally upwards, implying that it does not recharge the surrounding groundwater and has limited bank storage. 14C ages and Cl concentrations are well correlated and Cl concentrations may be used to provide a first-order estimate of groundwater residence times. Progressively lower chloride concentrations from 10 000 years BP to the present day are interpreted to indicate an increase in recharge rates on the Barongarook High. © Author(s) 2014

Speciation analysis of iodine and bromine at picogram-per-gram levels in polar ice

Iodine and bromine species participate in key atmospheric reactions including the formation of cloud con- densation nuclei and ozone depletion. We present a novel method coupling a high-performance liquid chromatogra- phy with ion chromatography and inductively coupled plas- ma mass spectrometry, which allows the determination of iodine (I) and bromine (Br) species (IO3−, I−, Br−, BrO3−) at the picogram-per-gram levels presents in Antarctic ice. Chromatographic separation was achieved using an ION- PAC® AS16 Analytical Column with NaOH as eluent. Detection limits for I and Br species were 5 to 9 pg g−1 with an uncertainty of less than 2.5% for all considered species. Inorganic iodine and bromine species have been determined in Antarctic ice core samples, with concentrations close to the detection limits for iodine species, and approximately 150 pg g−1 for Br−. Although iodate (IO3−) is the most abundant iodine species in the atmosphere, only the much rarer iodide (I−) species was present in Antarctic Holocene ice. Bromine was found to be present in Antarctic ice as Br−

Short-Lived Trace Gases in the Surface Ocean and the Atmosphere

The two-way exchange of trace gases between the ocean and the atmosphere is important for both the chemistry and physics of the atmosphere and the biogeochemistry of the oceans, including the global cycling of elements. Here we review these exchanges and their importance for a range of gases whose lifetimes are generally short compared to the main greenhouse gases and which are, in most cases, more reactive than them. Gases considered include sulphur and related compounds, organohalogens, non-methane hydrocarbons, ozone, ammonia and related compounds, hydrogen and carbon monoxide. Finally, we stress the interactivity of the system, the importance of process understanding for modeling, the need for more extensive field measurements and their better seasonal coverage, the importance of inter-calibration exercises and finally the need to show the importance of air-sea exchanges for global cycling and how the field fits into the broader context of Earth System Science

Determination of total and non-water soluble iodine in atmospheric aerosols by thermal extraction and spectrometric detection (TESI)

Iodine has recently been of interest in atmospheric chemistry due to its role in tropospheric ozone depletion, modification of the HO/HO2 ratio and aerosol nucleation. Gas-phase iodine chemistry is tightly coupled to the aerosol phase through heterogeneous reactions, which are dependent on iodine concentrations and speciation in the aerosol. To date, the only method available for total iodine determination in aerosols is collection on filters by impaction and quantification by neutron activation analysis (NAA). NAA is not widely available to all working groups and is costly to commission. Here, we present a method to determine total iodine concentrations in aerosol impact filter samples by combustion of filter sub-samples (~5 cm2) at 1,000 °C, trapping in deionised water and quantification by UV/Vis spectroscopy. Both quartz and cellulose filters were analysed from four separate sampling campaigns. The method proved to be sensitive (3s?=?6 ng absolute iodine?˜?3 pmol?m-3) precise (RSD?~?5%) and accurate, as determined by external and standard addition calibrations. Total iodine concentrations ranged from 10 pmol?m-3 over the Southern Ocean to 100 pmol?m-3 over the tropical Atlantic, in agreement with previous estimates. The soluble iodine concentration (extracted with water and measured by ICP-MS) was then subtracted from the total iodine to yield non-water-soluble iodine (NSI). The NSI fraction ranged from 20% to 53% of total iodine, and thus can be significant in some cases

Combining Radon and heat as tracers to characterise surface water andgroundwater exchange pathways

Heat and Radon (222-Rn) have both been used separately as natural tracers to quantify vertical streambed fluxes and to calculate water residence times in shallow alluvial systems. Both tracers have different advantages and limitations: Heat transport is measured through temperature changes at discrete spatial points in the streambed, and methods for the calculation of vertical flux time-series exist. By contrast, grab sampled Radon activities represent integration along a flow path but the discrete sampling means that only a snapshot in time can be obtained. A pumping test was conducted at Maules Creek (Australia) in order to artificially stress the stream-aquifer system. Water was continuously pumped from an extraction well located 40 m from the creek for 8 days. A flood event occurred during the pumping test adding another level of complexity to the system. The stream-aquifer response was monitored with a transect of 25 observation bores, of which 15 were regularly sampled for Radon activities. Additionally, a total of 4 temperature arrays, consisting of 4 temperature loggers each, were installed in the streambed to measure the sediment temperature over time. Vertical streambed fluxes were calculated using the temperature data. A joint interpretation of heat and Radon results reveals subsurface heterogeneity and distinct exchange pathways. This study shows the advantage of combining at least two different tracers in order to characterise a connected system

Fate of methane bubbles released by pockmarks in Lake Constance

In the eastern part of Lake Constance, the second largest pre-alpine Lake in Europe, about five hundred pockmarks (morphological depressions on the lake floor) were recently discovered of which ~ 40% release methane bubbles. The carbon isotopic composition of the escaping gas indicated that the methane is of biogenic origin. In our study, we investigated the fate of the released methane bubbles, i.e., the dissolution, oxidation or transport of the bubbles to the surface. At a littoral pockmark site (PM12, 12 m water depth) and a profundal pockmark (PM80, 80 m water depth), we analysed the dissolved methane concentrations and the methane isotopic carbon signature in the water column. At PM80, higher methane concentrations (up to 1523 nM), compared to the control site and the surface waters (225 ± 72 nM), were recorded only on some occasions and only in the bottom water, despite the fact that the released bubbles were dissolving within the hypolimnion based on bubble modeling. The isotope data suggest that most of the dissolved methane is oxidized below 40 m water depth. The isotopic signature of the methane in the surface water at PM80, however, differed from that of the methane in the hypolimnion; therefore, the surface methane at this profundal site is most likely an export product from the littoral zone. Assuming an initial bubble diameter of 5 mm, we calculated that these small bubbles would reach the surface, but approximately 96% of the methane would have dissolved from the bubble into the hypolimnion. At PM12, we observed higher concentrations of dissolved methane (312 ± 52 nM) with no significant differences between seasons or between control sites versus pockmark site. In the shallow water, divers estimated the bubble size to be 10 - 15 mm, which from a release depth of 12 m would barely dissolved in to the water column. The isotopic signature also indicated that there had been almost no methane oxidation in the shallow water column. Thus, the water depth of bubble release as well as the initial bubble size determine whether the methane enters the atmosphere largely unhindered (shallow site) or if the released methane is incorporated into the profundal water column