Groundwater dating with 3H and SF6 in relation to mixing patterns,transport modelling and hydrochemistry

A comprehensive study of a sandy aquifer of deltaic origin in southern Poland included water chemistry, isotopes, dissolved trace gases and transport modelling. Tritium, sulphur hexafluoride (SF₆) and freons (F‐11, F‐12 and F‐113) showed the presence of modern waters in the recharge areas and shallow confined parts of the aquifer. The presence of older Holocene waters farther from the recharge areas was indicated by lack of ³H, SF₆ contents ≤0·02 fmol l⁻¹ and relatively low ¹⁴C values. The discharge from the system is by upward seepage in the valley of a major river. Pre‐Holocene waters of a cooler climate, identified on the basis of δ¹⁸O, δ²H, ¹⁴C, Ne and Ar data, were found in some distant wells. Concentrations of N₂, Ne and Ar determined by gas chromatography were used for calculating the noble gas temperatures, air excess needed for correction of SF₆, and nitrogen content released by denitrification process. The time series of ³H content available for some wells supplied quantitative information on age distributions and the total mean ages of flow through the unsaturated and saturated zones. The derived ³H age distributions turned out to be very wide, with mean values in the range of about 30 to 160 years. For each well with determined ³H age, the SF₆ data showed either a lower age range or the possibility of a lower age as expected due to shorter travel times of SF₆ through the unsaturated zone, which most probably also resulted in different types of age distributions of these tracers. Freons appeared to be of little use for individual age determinations. A quantitative estimation of two‐component mixing from SF₆ ³H relations is not possible unless the travel time of ³H through the unsaturated zone is comparable to that of SF₆. The ratio of integrals of the response function over the age range with tracer and the whole response function yields the ratio of water with tracer to total flow of water. That ratio is a tracer‐dependent function of time. Transport modelling of SF₆ tracer done with MT3D code yielded initially large discrepancies between calculated and measured tracer concentrations. Some discrepancies remained even after calibration of the transport model with SF₆. Simulation of tritium contents with a calibrated transport model yielded reasonable agreement with measured contents in some wells and indicated a need for further investigations, particularly in the eastern part of the aquifer. The existence of distinct hydrochemical zones is consistent with the tracer data; young waters with measurable ³H and SF₆ contents are aerobic and of HCO₃ Ca or HCO₃ SO₄ Ca types. Slightly elevated Na and Cl contents, as well as the highest concentrations of SO₄ and NO₃ within this zone are due to anthropogenic influences. Anaerobic conditions prevail in the far field, under the confining cover, where pre‐bomb era Holocene waters dominate. In that zone, dissolved oxygen, NO₃ and U contents are reduced, and Fe, Mn and NH₄ contents increase. In the third zone, early Holocene and glacial waters occur. They are of HCO₃ Ca Na or HCO₃ Na types, with TDS values higher than 1 g l⁻¹ and Na content higher than 200 mg l⁻¹, due to either small admixtures of ascending or diffusing older water or freshening of marine sediments, a process that is probably occurring till the present time. Copyright © 2005 John Wiley & Sons, Ltd.