Stable isotopes of water and nitrate for the identification of groundwater flowpaths: A review

Nitrate contamination in stream water and groundwater is a serious environmental problem that arises in areas of high agricultural activities or high population density. It is therefore important to identify the source and flowpath of nitrate in water bodies. In recent decades, the dual isotope analysis (δ¹⁵N and δ¹⁸O) of nitrate has been widely applied to track contamination sources by taking advantage of the difference in nitrogen and oxygen isotope ratios for different sources. However, transformation processes of nitrogen compounds can change the isotopic composition of nitrate due to the various redox processes in the environment, which often makes it difficult to identify contaminant sources. To compensate for this, the stable water isotope of the H₂O itself can be used to interpret the complex hydrological and hydrochemical processes for the movement of nitrate contaminants. Therefore, the present study aims at understanding the fundamental background of stable water and nitrate isotope analysis, including isotope fractionation, analytical methods such as nitrate concentration from samples, instrumentation, and the typical ranges of δ¹⁵N and δ¹⁸O from various nitrate sources. In addition, we discuss hydrograph separation using the oxygen and hydrogen isotopes of water in combination with the nitrogen and oxygen isotopes of nitrate to understand the relative contributions of precipitation and groundwater to stream water. This study will assist in understanding the groundwater flowpaths as well as tracking the sources of nitrate contamination using the stable isotope analysis in combination with nitrate and water.