Changes in groundwater dissolved organic matter character in a coastal sand aquifer due to rainfall recharge

Dissolved organic matter (DOM) in groundwater is fundamentally important with respect to biogeochemical reactions, global carbon cycling, heavy metal transport, water treatability and potability. One source of DOM to groundwater is from the transport of organic matter from the vadose zone by rainfall recharge. Changes in precipitation patterns associated with natural climate variability and climate change are expected to alter the load and character of organic matter released from these areas, which ultimately impacts on groundwater quality and DOM treatability. In order to investigate potential changes in groundwater DOM character after rainfall recharge, we sampled shallow groundwater from a coastal peat-rich sand aquifer in New South Wales, Australia, during an extended period of low precipitation (average daily precipitation rate < 1.6 mm day^-1 over the 8 months prior to sampling), and after two heavy precipitation events (84 mm day^-1 and 98 mm day^-1 respectively). We assess changes in DOM composition after correcting for dilution by a novel combination of two advanced analytical techniques: liquid chromatography organic carbon detection (LC-OCD) and negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We also assess changes in water chemistry pre- and post-rainfall. Post-rainfall, we show that the dilution-corrected amount of highly aromatic DOM molecular formulae (i.e. those categorised into the groups polyphenolics and condensed aromatics) were 1.7 and 2.0 times higher respectively than in pre-rainfall samples. We attribute this to the flushing of peat-derived DOM from buried organic material into the groundwater. We also identify that periods of low precipitation can lead to low hydrophilic/HOC ratios in groundwater (median = 4.9, n = 14). Redundancy analysis (RDA) was used to compare the HOC fraction with FT-ICR MS compound groups. We show that HOC has a more aromatic character in pre-rainfall samples, and is less similar to the aromatic groups in post-rainfall samples. This suggests that the decline in water-borne hydrophobics observed post-rainfall could be associated with preferential adsorption of the hydrophobic aromatic DOM, making post-rainfall samples less treatable for potable water supply. Post-rainfall we also observe significant increases in arsenic (leading to concentrations greater than 3 times the World Health Organisation drinking water limit of 10 μg / L). Increases in coastal rainfall due to climate change may therefore alter the composition of groundwater DOM in coastal peatland areas in ways that may impact DOM bioavailability, and increase arsenic concentrations, reducing the ease of water treatment for human consumption. To the best of our knowledge, this is the first study to identify the chemical and molecular changes of shallow groundwater DOM pre-rainfall and post-rainfall in a sedimentary organic carbon rich environment through multiple analytical techniques.