Elucidation of denitrification mechanism in karstic Ryukyu limestone aquifer

Abstract:

Nitrate (NO₃⁻) concentrations in public water supplies have risen above acceptable levels in many areas of the world including Japan, largely as a result of contamination by human and animal waste and overuse of fertilizers. A previous study has characterized nitrate concentrations in groundwater in this area is a higher than the upper value (44mgL⁻¹) of environmental quality criteria on one hands. On the other hand, there exists points where the concentration of nitric acid is not detected, which suggests the possibility of denitrification. During early 2000, a new analytical procedure for nitrate isotopic measurement, termed the “denitrifier method”, was established. With the development of the nitrate isotope tracer method, much research has been reported detailing sources of groundwater nitrate and denitrification mechanisms. This study presents a pilot case study (in the southern part of Okinawa Main Island, Japan, where Ryukyu limestone is extensively distributed) using the combined stable isotope ratios of major elements (C, N and S) as net recorders of the biogeochemical reactions with the aim of elucidation of denitrification mechanism in Ryukyu limestone aquifer.

As a result, significant decreases in nitrate concentrations due to denitrification were observed in groundwater at some locations, which induced increases in isotope ratios up to 59.7‰ for δ¹⁵N_NO3. These points of groundwater were located above the cutoff wall of the underground dam and near the fault. It is considered that the residence time of the groundwater is longer than the other points at these denitrification points, and that reduction condition tends to be formed in the groundwater. However, the rapid rise of the groundwater level due to rainfall is likely to occur in the Ryukyu limestone aquifer, where the ground water was found to have changed dynamically from the reduction condition to the oxidation condition which a denitrification (has not occured)does not occur. Moreover, the occurrence of autotrophic denitrification was suggested by the δ¹⁵N_NO3，δ¹³C_DIC，and δ³⁴S_SO4 values in Ryukyu limestone aquifer.