Impact of urbanization on hydrochemical evolution of groundwater and on unsaturated-zone gas composition in the coastal city of Tel Aviv, Israel.

The coastal city of Tel Aviv was founded at the beginning of the 20th century. The number of its inhabitants and its water consumption increased rapidly. This study analyses a 15-year record (1934-1948) of pre-industrial development of groundwater chemistry in the urban area. Archive data on concentrations of major ions, dissolved gases (CO2 and O2), organic matter, and pH were available for each half-year during the period of 1934-1948. The major factors causing changes in the chemistry of groundwater flowing in three sandy sub-aquifers have been seawater encroachment due to overpumping, and infiltration of effluents from pit-latrine collectors. Influence of these factors decreases with depth. Landward-penetrating seawater passed through clayey coastal sediments, interbedded among sands and calcareous sandstones, and spread into the Kurkar Group aquifer. This has led to exchange of sodium (dominant in seawater) with calcium adsorbed on clay particles, enriching groundwater with calcium. Intensity of cation exchange decreases inland and with depth. Infiltration of pit-latrine effluents has introduced large amounts of ammonium into the unsaturated zone. Its rapid oxidation in unsaturated sediments has caused massive nitrate production, accompanied by pore-water acidification. This process induces dissolution of vadose carbonate, resulting in enrichment of groundwater recharge in calcium. Anthropogenically induced dissolution of calcite in the unsaturated zone has been the major factor for the increase of Ca2+ concentration in groundwater, accounting for about 80% of this increase. In the interface zone, an additional 20% of calcium has been supplied by cation exchange. Owing to pH increase caused by denitrification in the aquifer, Ca(2+)-rich waters supersaturated with calcite could be formed, especially in the capillary fringe of the uppermost sub-aquifer, which could induce calcite precipitation and ultimately lead to the cementation of sandy aquifers. Urban development has caused drastic changes in the gas content in the unsaturated zone and in groundwater. Carbon dioxide was intensively generated by nitrification-denitrification processes, by hydration of urea, to a lesser degree by oxidation of organic matter, and probably by anoxic biodegradation of organics. Between 1934 and 1948, concentrations of CO2 in unsaturated sediment air rose from 3.2% to 7.6%. In the unsaturated zone, oxygen consumption for oxidation of ammonium and organic matter lowered O2 concentrations in sediment air to unusually low values of 3.9-12.9%. Nitrification in the urban unsaturated zone could thus serve as a pump, sucking in atmospheric oxygen at a rate of about 0.3-0.5 g m-2 day-1. The extreme concentrations of CO2 and O2 in unsaturated sediments have been preserved due to production and consumption of gas under conditions of diminishing areas open to the atmosphere, uncovered by buildings and by roads.