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.

Stormwater Best Management Practices: Experimental Evaluation of Chemical Cocktails Mobilized by Freshwater Salinization Syndrome.

Freshwater Salinization Syndrome (FSS) refers to the suite of physical, biological, and chemical impacts of salt ions on the degradation of natural, engineered, and social systems. Impacts of FSS on mobilization of chemical cocktails has been documented in streams and groundwater, but little research has focused on the effects of FSS on stormwater best management practices (BMPs) such as: constructed wetlands, bioswales, ponds, and bioretention. However emerging research suggests that stormwater BMPs may be both sources and sinks of contaminants, shifting seasonally with road salt applications. We conducted lab experiments to investigate this premise; replicate water and soil samples were collected from four distinct stormwater feature types (bioretention, bioswale, constructed wetlands and retention ponds) and were used in salt incubation experiments conducted under six different salinities with three different salts (NaCl, CaCl2, and MgCl2). Increased salt concentrations had profound effects on major and trace element mobilization, with all three salts showing significant positive relationships across nearly all elements analyzed. Across all sites, mean salt retention was 34%, 28%, and 26% for Na+, Mg2+ and Ca2+ respectively, and there were significant differences among stormwater BMPs. Salt type showed preferential mobilization of certain elements. NaCl mobilized Cu, a potent toxicant to aquatic biota, at rates over an order of magnitude greater than both CaCl2 and MgCl2. Stormwater BMP type also had a significant effect on elemental mobilization, with ponds mobilizing significantly more Mn than other sites. However, salt concentration and salt type consistently had significant effects on mean concentrations of elements mobilized across all stormwater BMPs (p<0.05), suggesting that processes such as ion exchange mobilize metals mobilize metals and salt ions regardless of BMP type. Our results suggest that decisions regarding the amounts and types of salts used as deicers can have significant effects on reducing contaminant mobilization to freshwater ecosystems.

Freshwater Salinization Syndrome Alters Nitrogen Transport in Urban Watersheds.

Anthropogenic salt inputs have impacted many streams in the U.S. for over a century. Urban stream salinity is often chronically elevated and punctuated by episodic salinization events, which can last hours to days after snowstorms and the application of road salt. Here, we investigated the impacts of freshwater salinization on total dissolved nitrogen (TDN) and NO3-/NO2- concentrations and fluxes across time in urban watersheds in the Baltimore-Washington D.C. metropolitan area of the Chesapeake Bay region. Episodic salinization from road salt applications and snowmelt quickly mobilized TDN in streams likely through soil ion exchange, hydrologic flushing, and other biogeochemical processes. Previous experimental work from other studies has shown that salinization can mobilize nitrogen from sediments, but less work has investigated this phenomenon with high-frequency sensors and targeted monitoring during road salt events. We found that urban streams exhibited elevated concentrations and fluxes of TDN, NO3-/NO2-, and specific conductance that rapidly peaked during and after winter road salt events, and then rapidly declined afterwards. We observed plateaus in TDN concentrations in the ranges of the highest specific conductance values (between 1000 and 2000 µS/cm) caused by road salt events. Plateaus in TDN concentrations beyond a certain threshold of specific conductance values suggested source limitation of TDN in watersheds (at the highest ranges in chloride concentrations and ranges); salts were likely extracting nitrogen from soils and streams through ion exchange in soils and sediments, ion pairing in soils and waters, and sodium dispersion of soils to a certain threshold level. When watershed transport was compared across land use, including a forested reference watershed, there was a positive relationship between Cl- loads and NO3-/NO2- loads. This relationship occurred across all sites regardless of land use, which suggests that the mass transport of Cl- and NO3-/NO2- are likely influenced by similar factors such as soil ion exchange, ion pairing, sodium dispersion of soils, hydrologic flushing, and biogeochemical processes. Freshwater salinization has the potential to alter the magnitude and timing of total dissolved nitrogen delivery to receiving waters during winter months following road salt applications, and further work should investigate the seasonal relationships of N transport with salinization in urban watersheds.

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.

Tree Trade-Offs in Stream Restoration: Impacts on Riparian Groundwater Quality.

Riparian zones are a vital interface between land and stream and are often the focus of stream restoration efforts to reduce nutrient pollution in waterways. Restoration of degraded stream channels often requires the removal of mature trees during major physical alteration of the riparian zone to reshape streambank topography. We assessed the impact of tree removal on riparian groundwater quality over space and time. Twenty-nine wells were installed across 5 sites in watersheds of the Washington D.C. and Baltimore, Maryland, USA metropolitan areas. Study sites encompassed a chronosequence of restoration ages (5, 10 and 20 years) as well as unrestored comparisons. Groundwater wells were installed as transects of 3 perpendicular to the stream channel to estimate nutrient uptake along groundwater flow paths. Groundwater samples collected over a 2-year period (2018-2019) were analyzed for concentrations of dissolved inorganic carbon (DIC), dissolved organic carbon (DOC), total dissolved nitrogen (TDN), and dissolved components of calcium (Ca), potassium (K), magnesium (Mg), sodium (Na), sulfur (S) and other elements. Results showed some interesting patterns such as: (1) elevated concentrations of some nutrients and carbon in riparian groundwater of recently restored (5 year) sites; (2) decreasing linear trends in concentrations of TDN, K and S in groundwater during a 2 year shift from wet to dry conditions; (3) linear relationships between DOC (organic matter) and plant nutrients in groundwater suggesting the importance of plant uptake and biomass as sources and sinks of nutrients; (4) increasing concentrations in groundwater along hydrologic flow paths from uplands to streams in riparian zones where trees were recently cut, and opposite patterns where trees were not cut. Riparian zones appeared to act as sources or sinks of bioreactive elements based on tree removal. Mean TDN, DOC, and S, concentrations decreased by 78.6%, 12.3%, and 19.3% respectively through uncut riparian zones, but increased by 516.9%, 199.7%, and 34.5% respectively through the 5-year cut transects. Ecosystem recovery and an improvement in groundwater quality appeared to be achieved by 10-20 years after restoration. A better understanding of the effects of riparian tree removal on groundwater quality can inform strategies for minimizing unintended effects of stream restoration on groundwater chemistry.

Sensors track mobilization of 'chemical cocktails' in streams impacted by road salts in the Chesapeake Bay watershed.

Increasing trends in base cations, pH, and salinity of freshwaters have been documented in U.S. streams over 50 years. These patterns, collectively known as Freshwater Salinization Syndrome (FSS), are driven by multiple processes, including applications of road salt and human-accelerated weathering of impervious surfaces, reductions in acid rain, and other anthropogenic legacies of change. FSS mobilizes chemical cocktails of distinct elemental mixtures via ion exchange, and other biogeochemical processes. We analyzed impacts of FSS on streamwater chemistry across five urban watersheds in the Baltimore-Washington, USA metropolitan region. Through combined grab-sampling and high-frequency monitoring by USGS sensors, regression relationships were developed among specific conductance and major ion and trace metal concentrations. These linear relationships were statistically significant in most of the urban streams (e.g., R2 = 0.62 and 0.43 for Mn and Cu, respectively), and showed that specific conductance could be used as a proxy to predict concentrations of major ions and trace metals. Major ions and trace metals analyzed via linear regression and principal component analysis (PCA) showed co-mobilization (i.e., correlations among combinations of specific conductance, Mn, Cu, Sr2+, and all base cations during certain times of year and hydrologic conditions). Co-mobilization of metals and base cations was strongest during peak snow events but could continue over 24 hours after specific conductance peaked, suggesting ongoing cation exchange in soils and stream sediments. Mn and Cu concentrations predicted from specific conductance as a proxy indicated acceptable goodness of fit for predicted vs. observed values (Nash-Sutcliffe Efficiency > 0.28). Metals concentrations remained elevated for days after specific conductance decreased following snowstorms, suggesting lag times and continued mobilization after road salt use. High-frequency sensor monitoring and proxies associated with FSS may help better predict contaminant pulses and contaminant exceedances in response to salinization and impacts on aquatic life, infrastructure, and drinking water.

Making 'Chemical Cocktails' - Evolution of Urban Geochemical Processes across the Periodic Table of Elements.

Urbanization contributes to the formation of novel elemental combinations and signatures in terrestrial and aquatic watersheds, also known as 'chemical cocktails.' The composition of chemical cocktails evolves across space and time due to: (1) elevated concentrations from anthropogenic sources, (2) accelerated weathering and corrosion of the built environment, (3) increased drainage density and intensification of urban water conveyance systems, and (4) enhanced rates of geochemical transformations due to changes in temperature, ionic strength, pH, and redox potentials. Characterizing chemical cocktails and underlying geochemical processes is necessary for: (1) tracking pollution sources using complex chemical mixtures instead of individual elements or compounds; (2) developing new strategies for co-managing groups of contaminants; (3) identifying proxies for predicting transport of chemical mixtures using continuous sensor data; and (4) determining whether interactive effects of chemical cocktails produce ecosystem-scale impacts greater than the sum of individual chemical stressors. First, we discuss some unique urban geochemical processes which form chemical cocktails, such as urban soil formation, human-accelerated weathering, urban acidification-alkalinization, and freshwater salinization syndrome. Second, we review and synthesize global patterns in concentrations of major ions, carbon and nutrients, and trace elements in urban streams across different world regions and make comparisons with reference conditions. In addition to our global analysis, we highlight examples from some watersheds in the Baltimore-Washington DC region, which show increased transport of major ions, trace metals, and nutrients across streams draining a well-defined land-use gradient. Urbanization increased the concentrations of multiple major and trace elements in streams draining human-dominated watersheds compared to reference conditions. Chemical cocktails of major and trace elements were formed over diurnal cycles coinciding with changes in streamflow, dissolved oxygen, pH, and other variables measured by high-frequency sensors. Some chemical cocktails of major and trace elements were also significantly related to specific conductance (p<0.05), which can be measured by sensors. Concentrations of major and trace elements increased, peaked, or decreased longitudinally along streams as watershed urbanization increased, which is consistent with distinct shifts in chemical mixtures upstream and downstream of other major cities in the world. Our global analysis of urban streams shows that concentrations of multiple elements along the Periodic Table significantly increase when compared with reference conditions. Furthermore, similar biogeochemical patterns and processes can be grouped among distinct mixtures of elements of major ions, dissolved organic matter, nutrients, and trace elements as chemical cocktails. Chemical cocktails form in urban waters over diurnal cycles, decades, and throughout drainage basins. We conclude our global review and synthesis by proposing strategies for monitoring and managing chemical cocktails using source control, ecosystem restoration, and green infrastructure. We discuss future research directions applying the watershed chemical cocktail approach to diagnose and manage environmental problems. Ultimately, a chemical cocktail approach targeting sources, transport, and transformations of different and distinct elemental combinations is necessary to more holistically monitor and manage the emerging impacts of chemical mixtures in the world's fresh waters.

Novel 'chemical cocktails' in inland waters are a consequence of the freshwater salinization syndrome.

Widespread changes in water temperatures, salinity, alkalinity and pH have been documented in inland waters in North America, which influence ion exchange, weathering rates, chemical solubility and contaminant toxicity. Increasing major ion concentrations from pollution, human-accelerated weathering and saltwater intrusion contribute to multiple ecological stressors such as changing ionic strength and pH and mobilization of chemical mixtures resulting in the freshwater salinization syndrome (FSS). Here, we explore novel combinations of elements, which are transported together as chemical mixtures containing salts, nutrients and metals as a consequence of FSS. First, we show that base cation concentrations have increased in regions primarily in North America and Europe over 100 years. Second, we show interactions between specific conductance, pH, nitrate and metals using data from greater than 20 streams located in different regions of the USA. Finally, salinization experiments and routine monitoring demonstrate mobilization of chemical mixtures of cations, metals and nutrients in 10 streams draining the Washington, DC-Baltimore, MD metropolitan regions. Freshwater salinization mobilizes diverse chemical mixtures influencing drinking water quality, infrastructure corrosion, freshwater CO2 concentrations and biodiversity. Most regulations currently target individual contaminants, but FSS requires managing mobilization of multiple chemical mixtures and interacting ecological stressors as consequences of freshwater salinization.This article is part of the theme issue 'Salt in freshwaters: causes, ecological consequences and future prospects'.

Watershed 'Chemical Cocktails': Forming Novel Elemental Combinations in Anthropocene Fresh Waters.

In the Anthropocene1, watershed chemical transport is increasingly dominated by novel combinations elements, which are hydrologically linked together as 'chemical cocktails.' Chemical cocktails are novel because human activities greatly enhance elemental concentrations and their probability for biogeochemical interactions and shared transport along hydrologic flowpaths. A new chemical cocktail approach advances our ability to: trace contaminant mixtures in watersheds, develop chemical proxies with high-resolution sensor data, and manage multiple water quality problems. We explore the following questions: (1) Can we classify elemental transport in watersheds as chemical cocktails using a new approach? (2) What is the role of climate and land use in enhancing the formation and transport of chemical cocktails in watersheds? To address these questions, we first analyze trends in concentrations of carbon, nutrients, metals, and salts in fresh waters over 100 years. Next, we explore how climate and land use enhance the probability of formation of chemical cocktails of carbon, nutrients, metals, and salts. Ultimately, we classify transport of chemical cocktails based on solubility, mobility, reactivity, and dominant phases: (1) sieved chemical cocktails (e.g., particulate forms of nutrients, metals and organic matter); (2) filtered chemical cocktails (e.g., dissolved organic matter and associated metal complexes); (3) chromatographic chemical cocktails (e.g., ions eluted from soil exchange sites); and (4) reactive chemical cocktails (e.g., limiting nutrients and redox sensitive elements). Typically, contaminants are regulated and managed one element at a time, even though combinations of elements interact to influence many water-quality problems such as toxicity to life, eutrophication, infrastructure and water treatment. A chemical cocktail approach significantly expands evaluations of water-quality signatures and impacts beyond single elements to mixtures. High-frequency sensor data (pH, specific conductance, turbidity, etc.) can serve as proxies for chemical cocktails and improve real-time analyses of water-quality violations, identify regulatory needs, and track water quality recovery following and extreme climate events. Ultimately, a watershed chemical cocktail approach is necessary for effectively co-managing groups of contaminants and provides a more holistic approach for studying, monitoring, and managing water quality in the Anthropocene.