Abstract

The chemical and isotopic composition of groundwater from 52 sites in the London (U.K.) area was determined as part of a project aimed at assessing the spatial variation in the age of Chalk groundwater, and in determining the relationship between fracture and matrix groundwater in this dual porosity system. Systematic changes in groundwater chemistry take place in the downgradient direction in response to several chemical processes. These processes include early concentration by evaporation and congruent dissolution of calcite followed by widespread incongruent dissolution and ion exchange in addition to local oxidation-reduction reactions, gypsum dissolution and saline intrusion. As a result of the above processes, Chalk groundwater follows an evolutionary path from Ca bicarbonate type to Na bicarbonate type. The age of Chalk groundwater was modelled using 14C, δ 13C , 3H, δ 2H and δ 180 . There is a general increase in the groundwater age in a downgradient direction with the oldest water found in N central areas of the basin. Groundwater in the unconfined zones and in areas S of the Greenwich fault is almost entirely of unevolved, modem composition. Carbon-14 modelling suggests that Chalk groundwater in the S basin is generally less than 10000 a old while that in the north is generally between 10000 and 25000 a old. The presence of 3H in concentrations of up to 7 TU in groundwater which yields ages of several 1000 a, however, indicates that mechanisms exist for the rapid introduction of recent groundwater to the confined aquifer. Results of palaeorecharge temperature determinations using δ 2H, δ 180 and noble gas analytical results suggest that significant Devensian recharge did indeed occur in the aquifer. A model of the development of the Chalk recognizes that it is a classic dual porosity aquifer in which groundwater flow occurs predominantly in the fracture system. The upper 50 m of the aquifer was flushed with fresh water during the 2–3 × 10 6 a of the Quaternary and therefore meteoric water largely replaced the Tertiary and Cretaceous marine water that previously saturated the system. Most processes which control the chemistry of the groundwater occur in the matrix where the surface area is exceptionally high. Although fracture flow dominates the flow regime, diffusion from the matrix into the fracture porosity controls the chemistry of Chalk groundwater.

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