The movement of water, matter, organisms, and energy can be altered substantially at ecohydrological interfaces, the dynamic transition zones that often develop within ecotones or boundaries between adjacent ecosystems. Interdisciplinary research over the last two decades has indicated that ecohydrological interfaces are often “hot spots” of ecological, biogeochemical, and hydrological processes and may provide refuge for biota during extreme events. Ecohydrological interfaces can have significant impact on global hydrological and biogeochemical cycles, biodiversity, pollutant removal, and ecosystem resilience to disturbance. The organizational principles (i.e., the drivers and controls) of spatially and temporally variable processes at ecohydrological interfaces are poorly understood and require the integrated analysis of hydrological, biogeochemical, and ecological processes. Our rudimentary understanding of the interactions between different drivers and controls critically limits our ability to predict complex system responses to change. In this paper, we explore similarities and contrasts in the functioning of diverse freshwater ecohydrological interfaces across spatial and temporal scales. We use this comparison to develop an integrated, interdisciplinary framework, including a roadmap for analyzing ecohydrological processes and their interactions in ecosystems. We argue that, in order to fully account for their nonlinear process dynamics, ecohydrological interfaces need to be conceptualized as unique, spatially and temporally dynamic entities, which represents a step change from their current representation as boundary conditions at investigated ecosystems.

Chlorinated ethenes (CEs) are legacy contaminants whose chemical footprint is expected to persist in aquifers around the world for many decades to come. These organohalides have been reported in river systems with concerning prevalence and are thought to be significant chemical stressors in urban water ecosystems. The aquifer-river interface (known as the hyporheic zone) is a critical pathway for CE discharge to surface water bodies in groundwater baseflow. This pore water system may represent a natural bioreactor where anoxic and oxic biotransformation process act in synergy to reduce or even eliminate contaminant fluxes to surface water. Here, we critically review current process understanding of anaerobic CE respiration in the competitive framework of hyporheic zone biogeochemical cycling fuelled by in-situ fermentation of natural organic matter. We conceptualise anoxic-oxic interface development for metabolic and co-metabolic mineralisation by a range of aerobic bacteria with a focus on vinyl chloride degradation pathways. The superimposition of microbial metabolic processes occurring in sediment biofilms and bulk solute transport delivering reactants produces a scale dependence in contaminant transformation rates. Process interpretation is often confounded by the natural geological heterogeneity typical of most riverbed environments. We discuss insights from recent field experience of CE plumes discharging to surface water and present a range of practical monitoring technologies which address this inherent complexity at different spatial scales. Future research must address key dynamics which link supply of limiting reactants, residence times and microbial ecophysiology to better understand the natural attenuation capacity of hyporheic systems.

Dynamic impact to the water environment of deicing salt application at a major highway (motorway) interchange in the UK is quantitatively evaluated for two recent severe UK winters. The contaminant transport pathway studied allowed controls on dynamic highway runoff and storm-sewer discharge to a receiving stream and its subsequent leakage to an underlying sandstone aquifer, including possible contribution to long-term chloride increases in supply wells, to be evaluated. Logged stream electrical-conductivity (EC) to estimate chloride concentrations, stream flow, climate and motorway salt application data were used to assess salt fate. Stream loading was responsive to salt applications and climate variability influencing salt release. Chloride (via EC) was predicted to exceed the stream Environmental Quality Standard (250mg/l) for 33% and 18% of the two winters. Maximum stream concentrations (3500mg/l, 15% sea water salinity) were ascribed to salt-induced melting and drainage of highway snowfall without dilution from, still frozen, catchment water. Salt persistance on the highway under dry-cold conditions was inferred from stream observations of delayed salt removal. Streambed and stream-loss data demonstrated chloride infiltration could occur to the underlying aquifer with mild and severe winter stream leakage estimated to account for 21 to 54% respectively of the 70t of increased chloride (over baseline) annually abstracted by supply wells. Deicing salt infiltration lateral to the highway alongside other urban/natural sources were inferred to contribute the shortfall. Challenges in quantifying chloride mass/fluxes (flow gauge accuracy at high flows, salt loading from other roads, weaker chloride-EC correlation at low concentrations), may be largely overcome by modest investment in enhanced data acquisition or minor approach modification. The increased understanding of deicing salt dynamic loading to the water environment obtained is relevant to improved groundwater resource management, highway salt application practice, surface-water - ecosystem management, and decision making on highway drainage to ground.

Countries located on the East African Rift System (EARS) are vulnerable to fluoride in their groundwater; a vulnerability for the developing country of Malawi at the southern rift periphery that is not well characterised. Groundwater fluoride occurrence in Malawi is documented here to better understand and manage fluoride risks posed. Available literature and Gov't of Malawi archive fluoride data spanning some fifty years have been collated and augmented by our own 2016-18 surveys of groundwater quality in Southern Malawi, targeting deep-sourced springs. In total, fluoride data for 1365 borehole, spring and hot spring samples were assembled. Statistically, 83% of samples were below the 1.5 mg/l WHO limit, concentrations in the 1.5-6 mg/l range between former (pre-1993) and current WHO guidelines at 14%, and those with fluoride above the current Malawi (former WHO) 6 mg/l guideline, at 3%. A lower occurrence than in other zones of the EARS, but indicative of a need for a Malawi Gov't management policy revision and associated management strategies endorsed by several documented incidences of dental fluorosis in proximity to high fluoride groundwater. Increased fluoride is related to increased groundwater temperatures signifying the importance of geothermal groundwater provenance. Temperature data may indeed be used as a proxy indicator of fluoride risk; samples with a temperature >32 °C, contained >6 mg/l fluoride. Structural geological controls appear to allow deep geothermal groundwaters to come to the near surface, as evidenced by increased fluoride in springs and boreholes close to faulted areas. Hydrochemical evaluation shows that fluoride concentrations are influenced by fluorite equilibration and sensitivity to calcium and pH. Recommendations are made to further document the occurrence of fluoride and enhance management of risks due to fluoride in drinking water in Malawi. With fluoride as a key indicator within Sustainable Development Goal number 6, the current Malawi standard and waters with concentration between 1.5 and 6 mg/l will come under increased scrutiny and pose a key challenge to assessment and management efforts.