To
unravel the crucial components of natural organic matter that
respond to the process of anthropogenic groundwater recharge (AGR)
from different recharge water sources, dissolved organic matter (DOM)
and base-extractable particulate organic matter (POM) in groundwater
and surface water were analyzed using excitation–emission matrix
spectroscopy coupled with parallel factor analysis (EEM–PARAFAC).
The EEM and traditional spectral indices of samples show that the
fluorescent intensity, molecular weight, and humification degree of
the DOM were relatively higher than those of the POM, and the groundwater
in the reclaimed water recharge area (RWRA) was more contaminated
than in the south-to-north water recharge area (SNWRA). PARAFAC analysis
indicates that the DOM was dominated by an allochthonous humic-like
substance (C1), whereas the POM was dominated by tryptophan-like substances
associated with microbial activity (C2). Partitioning of PARAFAC components
between DOM and POM showed that the humic-like substances (C1 and
C4) were more likely to be distributed into a dissolved phase compared
to the protein-like substances (C2 and C3), which suggested the potential
use of C1 and C4 as a tracking indicator. In particular, the clear
gradient distributions along both the hydrogeological profile and
different aquifer systems in terms of the concentration and composition
of C1 also discriminated between the RWRA and SNWRA with regard to
the effects of various AGRs on the groundwater. The association between
C1 and water-quality indicators revealed by principal component analysis
further indicated that refractory humic-like substances would track
the environmental impacts of intentional AGR processes.