Hydrochemical Relation Between Shallow Groundwater with Elevated Fluoride and Groundwater in Underlying Carbonates

In the arid to semi-arid district of Chengcheng, Weinan City, in central Shaanxi Province, diminishing groundwater reserves in the shallow Quaternary (QLB) aquifer and elevated fluoride in the similarly shallow Permo-Triassic (PTF) aquifer, have promoted interest in the development of groundwater resources in the deep but poorly understood Cambrian-Ordovician carbonate aquifer system (COC). To investigate the origin of the COC groundwaters and the relationship between the deep and shallower systems, a hydrochemical study was undertaken involving 179 major and minor ion analyses, 39 stable isotope analyses (δD and δ¹⁸ O), and 14 carbon isotope analyses (¹⁴ C and δ¹³ C). PHREEQC 3.0 was used to investigate mixing. Hydrochemical data support the presence of a well-connected regional flow system extending southwards from the more mountainous north. Stable isotope data indicate that the COC groundwaters originate as soil zone infiltration, under a much cooler regime than is found locally today. This is confirmed by ¹⁴ C, which indicates the groundwater to be palaeowater recharged during the late Pleistocene (∼10-12 ka B.P.). The presence of nitrate in the COC groundwaters suggests leakage from overlying shallow aquifers currently provides an additional source of COC recharge, with major faults possibly providing the primary pathways for downward vertical flow.