Freshwater salinization syndrome limits management efforts to improve water quality.

Freshwater Salinization Syndrome (FSS) refers to groups of biological, physical, and chemical impacts which commonly occur together in response to salinization. FSS can be assessed by the mobilization of chemical mixtures, termed "chemical cocktails", in watersheds. Currently, we do not know if salinization and mobilization of chemical cocktails along streams can be mitigated or reversed using restoration and conservation strategies. We investigated 1) the formation of chemical cocktails temporally and spatially along streams experiencing different levels of restoration and riparian forest conservation and 2) the potential for attenuation of chemical cocktails and salt ions along flowpaths through conservation and restoration areas. We monitored high-frequency temporal and longitudinal changes in streamwater chemistry in response to different pollution events (i.e., road salt, stormwater runoff, wastewater effluent, and baseflow conditions) and several types of watershed management or conservation efforts in six urban watersheds in the Chesapeake Bay watershed. Principal component analysis (PCA) indicates that chemical cocktails which formed along flowpaths (i.e., permanent reaches of a stream) varied due to pollution events. In response to winter road salt applications, the chemical cocktails were enriched in salts and metals (e.g., Na+, Mn, and Cu). During most baseflow and stormflow conditions, chemical cocktails were less enriched in salt ions and trace metals. Downstream attenuation of salt ions occurred during baseflow and stormflow conditions along flowpaths through regional parks, stream-floodplain restorations, and a national park. Conversely, chemical mixtures of salt ions and metals, which formed in response to multiple road salt applications or prolonged road salt exposure, did not show patterns of rapid attenuation downstream. Multiple linear regression was used to investigate variables that influence changes in chemical cocktails along flowpaths. Attenuation and dilution of salt ions and chemical cocktails along stream flowpaths was significantly related to riparian forest buffer width, types of salt pollution, and distance downstream. Although salt ions and chemical cocktails can be attenuated and diluted in response to conservation and restoration efforts at lower concentration ranges, there can be limitations in attenuation during road salt events, particularly if storm drains bypass riparian buffers.

Five state factors control progressive stages of freshwater salinization syndrome.

Factors driving freshwater salinization syndrome (FSS) influence the severity of impacts and chances for recovery. We hypothesize that spread of FSS across ecosystems is a function of interactions among five state factors: human activities, geology, flowpaths, climate, and time. (1) Human activities drive pulsed or chronic inputs of salt ions and mobilization of chemical contaminants. (2) Geology drives rates of erosion, weathering, ion exchange, and acidification-alkalinization. (3) Flowpaths drive salinization and contaminant mobilization along hydrologic cycles. (4) Climate drives rising water temperatures, salt stress, and evaporative concentration of ions and saltwater intrusion. (5) Time influences consequences, thresholds, and potentials for ecosystem recovery. We hypothesize that state factors advance FSS in distinct stages, which eventually contribute to failures in systems-level functions (supporting drinking water, crops, biodiversity, infrastructure, etc.). We present future research directions for protecting freshwaters at risk based on five state factors and stages from diagnosis to prognosis to cure.

Longitudinal stream synoptic monitoring tracks chemicals along watershed continuums: a typology of trends.

There are challenges in monitoring and managing water quality due to spatial and temporal heterogeneity in contaminant sources, transport, and transformations. We demonstrate the importance of longitudinal stream synoptic (LSS) monitoring, which can track combinations of water quality parameters along flowpaths across space and time. Specifically, we analyze longitudinal patterns of chemical mixtures of carbon, nutrients, greenhouse gasses, salts, and metals concentrations along 10 flowpaths draining 1,765 km2 of the Chesapeake Bay region. These 10 longitudinal stream flowpaths are drained by watersheds experiencing either urban degradation, forest and wetland conservation, or stream and floodplain restoration. Along the 10 longitudinal stream flowpaths, we monitored over 300 total sampling sites along a combined stream length of 337 km. Synoptic monitoring along longitudinal flowpaths revealed: (1) increasing, decreasing, piecewise, or no trends and transitions in water quality with increasing distance downstream, which provide insights into water quality processes along flowpaths; (2) longitudinal trends and transitions in water quality along flowpaths can be quantified and compared using simple linear and non-linear statistical relationships with distance downstream and/or land use/land cover attributes, (3) attenuation and transformation of chemical cocktails along flowpaths depend on: spatial scales, pollution sources, and transitions in land use and management, hydrology, and restoration. We compared our LSS patterns with others from the global literature to synthesize a typology of longitudinal water quality trends and transitions in streams and rivers based on hydrological, biological, and geochemical processes. Applications of LSS monitoring along flowpaths from our results and the literature reveal: (1) if there are shifts in pollution sources, trends, and transitions along flowpaths, (2) which pollution sources can spread further downstream to sensitive receiving waters such as drinking water supplies and coastal zones, and (3) if transitions in land use, conservation, management, or restoration can attenuate downstream transport of pollution sources. Our typology of longitudinal water quality responses along flowpaths combines many observations across suites of chemicals that can follow predictable patterns based on watershed characteristics. Our typology of longitudinal water quality responses also provides a foundation for future studies, watershed assessments, evaluating watershed management and stream restoration, and comparing watershed responses to non-point and point pollution sources along streams and rivers. LSS monitoring, which integrates both spatial and temporal dimensions and considers multiple contaminants together (a chemical cocktail approach), can be a comprehensive strategy for tracking sources, fate, and transport of pollutants along stream flowpaths and making comparisons of water quality patterns across different watersheds and regions.

The Anthropogenic Salt Cycle.

Increasing salt production and use is shifting the natural balances of salt ions across Earth systems, causing interrelated effects across biophysical systems collectively known as freshwater salinization syndrome. In this Review, we conceptualize the natural salt cycle and synthesize increasing global trends of salt production and riverine salt concentrations and fluxes. The natural salt cycle is primarily driven by relatively slow geologic and hydrologic processes that bring different salts to the surface of the Earth. Anthropogenic activities have accelerated the processes, timescales and magnitudes of salt fluxes and altered their directionality, creating an anthropogenic salt cycle. Global salt production has increased rapidly over the past century for different salts, with approximately 300 Mt of NaCl produced per year. A salt budget for the USA suggests that salt fluxes in rivers can be within similar orders of magnitude as anthropogenic salt fluxes, and there can be substantial accumulation of salt in watersheds. Excess salt propagates along the anthropogenic salt cycle, causing freshwater salinization syndrome to extend beyond freshwater supplies and affect food and energy production, air quality, human health and infrastructure. There is a need to identify environmental limits and thresholds for salt ions and reduce salinization before planetary boundaries are exceeded, causing serious or irreversible damage across Earth systems.

Freshwater Salinization Syndrome Alters Retention and Release of 'Chemical Cocktails' along Flowpaths: from Stormwater Management to Urban Streams.

We investigate impacts of Freshwater Salinization Syndrome (FSS) on mobilization of salts, nutrients, and metals in urban streams and stormwater BMPs by analyzing original data on concentrations and fluxes of salts, nutrients, and metals from 7 urban watersheds in the Mid-Atlantic U.S. and synthesizing literature data. We also explore future critical research needs through a survey of practitioners and scientists. Our original data show: (1) sharp pulses in concentrations of salt ions and metals in urban streams directly following both road salt events and stream restoration construction (e.g., similar to the way concentrations increase during other soil disturbance activities); (2) sharp declines in pH (acidification) in response to road salt applications due to mobilization of H+ from soil exchange sites by Na+; (3) sharp increases in organic matter from microbial and algal sources (based on fluorescence spectroscopy) in response to road salt applications likely due to lysing cells and/or changes in solubility; (4) significant retention (~30-40%) of Na+ in stormwater BMP sediments and floodplains in response to salinization; (5) increased ion exchange and mobilization of diverse salt ions (Na+, Ca2+, K+, Mg2+), nutrients (N, P), and trace metals (Cu, Sr) from stormwater BMPs and restored streams in response to FSS; (6) downstream increasing loads of Cl-, SO4 2-, Br-, F-, and I- along flowpaths through urban streams, and P release from urban stormwater BMPs in response to salinization, and (7) a significant annual reduction (> 50%) in Na+ concentrations in an urban stream when road salt applications were dramatically reduced, which suggests potential for ecosystem recovery. We compared our original results to published metrics of contaminant retention and release across a broad range of stormwater management BMPs from North America and Europe. Overall, urban streams and stormwater management BMPs consistently retain Na+ and Cl- but mobilize multiple contaminants based on salt types and salinity levels. Finally, we present our top 10 research questions regarding FSS impacts on urban streams and stormwater management BMPs. Reducing diverse 'chemical cocktails' of contaminants mobilized by freshwater salinization is now a priority for effectively and holistically restoring urban waters.