Dissolved organic matter plays an important role in aquatic ecosystems and poses a major problem for drinking water production. However, our understanding of DOM reactivity in natural systems is hampered by its complex molecular composition. Here, we used Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and data from two independent studies to disentangle DOM reactivity based on photochemical and microbial-induced transformations. Robust correlations of FT-ICR-MS peak intensities with chlorophyll a and solar irradiation were used to define 9 reactivity classes for 1277 common molecular formulas. Germany’s largest drinking water reservoir was sampled for 1 year, and DOM processing in stratified surface waters could be attributed to photochemical transformations during summer months. Microbial DOM alterations could be distinguished based on correlation coefficients with chlorophyll a and often shared molecular features (elemental ratios and mass) with photoreactive compounds. In particular, many photoproducts and some microbial products were identified as potential precursors of disinfection byproducts. Molecular DOM features were used to further predict molecular reactivity for the remaining compounds in the data set based on a random forest model. Our method offers an expandable classification approach to integrate the reactivity of DOM from specific environments and link it to molecular properties and chemistry.

Photochemical processing is an important way to transform terrestrial dissolved organic matter (DOM) but was rarely investigated by ultra-high resolution mass spectrometry. We performed an irradiation experiment with water from a shaded forest stream flowing into a lit reservoir. Bacterial activity explained only 1% of dissolved organic carbon (DOC) decline in a combined bacterial and photodegradation approach. Photodegradation decreased the DOC concentration by 30%, the specific ultraviolet (UV) absorption by 40%–50%, and fluorescence intensity by 80% during six days. The humification index (HIX) decreased whereas the fluorescence index (FI) did not change. Two humic-like components identified by parallel factor analysis (PARAFAC) of excitation–emission matrices followed the decrease of fluorescent DOM. Changes of relative peak intensities of Fourier transform-ion cyclotron resonance mass spectroscopy (FT-ICR MS) elemental formula components as a function of cumulated radiation were evaluated both by Spearman’s rank correlation and linear regression. The FT-ICR MS intensity changes indicate that high aromatic material was photochemically converted into smaller non-fluorescent molecules or degraded by the release of CO2. This study shows the molecular change of terrestrial DOM before the preparation of drinking water from reservoirs.

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Abstract. Despite being the main drinking water resource for over five million people, the water balance of the Eastern Mountain Aquifer system on the western side of the Dead Sea is poorly understood. The regional aquifer consists of fractured and karstified limestone – aquifers of Cretaceous age and can be separated in Cenomanian aquifer (upper aquifer) and Albian aquifer (lower aquifer). Both aquifers are exposed along the mountain ridge around Jerusalem, which is the main recharge area. From here, the recharged groundwater flows in a highly karstified aquifer system towards the east, to discharge in springs in the Lower Jordan Valley and Dead Sea region. We investigated the Eastern Mountain Aquifer system on groundwater flow, groundwater age and potential mixtures, and groundwater recharge. We combined 36Cl/Cl, tritium and the anthropogenic gases SF6, CFC-12 and CFC-11, CFC-113 as dating tracers to estimate the young water components inside the Eastern Mountain Aquifer system. By application of lumped parameter models, we verified young groundwater components from the last 10 to 30 years and an admixture of a groundwater component older than about 70 years. Concentrations of nitrate, Simazine® (Pesticide), Acesulfame K® (artificial sweetener) and Naproxen® (drug) in the groundwater were further indications of infiltration during the last 30 years. The combination of multiple environmental tracers and lumped parameter modelling helped to understand the groundwater age distribution and to estimate recharge despite scarce data in this very complex hydrogeological setting. Our groundwater recharge rates support groundwater management of this politically difficult area and can be used to inform and calibrate ongoing groundwater flow models.

The Mataranka Springs Complex is the headwater of the iconic Roper River of northern Australia. Using environmental tracers measured in springs and nearby boreholes, the origin of groundwater contributing to the springs was evaluated to help assess the impact of proposed groundwater extraction in the Cambrian Limestone Aquifer (CLA) for irrigation agriculture and for hydraulic fracturing in the Beetaloo Sub-basin (an anticipated world-class unconventional gas reserve). Major ions, Sr, 87Sr/86Sr, δ18O-H2O, δ2H-H2O, 3H, 14C-DIC were consistent with regional groundwater from the Daly and Georgina basins of the CLA as the sources of water sustaining the major springs (Rainbow and Bitter) and one of the minor springs (Warloch Pond). However, 3H = 0.34 TU in another minor spring (Fig Tree) indicated an additional contribution from a young (probably local) source. High concentrations of radiogenic 4He (> 10–7 cm3 STP g–1) at Rainbow Spring, Bitter Spring and in nearby groundwater also indicated an input of deeper, older groundwater. The presence of older groundwater within the CLA demonstrates the need for an appropriate baseline characterisation of the vertical exchange of groundwater in Beetaloo Sub-basin ahead of unconventional gas resource development.