Salty chemical cocktails as water quality signatures: Longitudinal trends and breakpoints along different U.S. streams.

Along urban streams and rivers, various processes, including road salt application, sewage leaks, and weathering of the built environment, contribute to novel chemical cocktails made up of metals, salts, nutrients, and organic matter. In order to track the impacts of urbanization and management strategies on water quality, we conducted longitudinal stream synoptic (LSS) monitoring in nine watersheds in five major metropolitan areas of the U.S. During each LSS monitoring survey, 10-53 sites were sampled along the flowpath of streams as they flowed along rural to urban gradients. Results demonstrated that major ions derived from salts (Ca2+, Mg2+, Na+, and K+) and correlated elements (e.g. Sr2+, N, Cu) formed 'salty chemical cocktails' that increased along rural to urban flowpaths. Salty chemical cocktails explained 46.1% of the overall variability in geochemistry among streams and showed distinct typologies, trends, and transitions along flowpaths through metropolitan regions. Multiple linear regression predicted 62.9% of the variance in the salty chemical cocktails using the six following significant drivers (p < 0.05): percent urban land, wastewater treatment plant discharge, mean annual precipitation, percent silicic residual material, percent volcanic material, and percent carbonate residual material. Mean annual precipitation and percent urban area were the most important in the regression, explaining 29.6% and 13.0% of the variance. Different pollution sources (wastewater, road salt, urban runoff) in streams were tracked downstream based on salty chemical cocktails. Streams flowing through stream-floodplain restoration projects and conservation areas with extensive riparian forest buffers did not show longitudinal increases in salty chemical cocktails, suggesting that there could be attenuation via conservation and restoration. Salinization represents a common urban water quality signature and longitudinal patterns of distinct chemical cocktails and ionic mixtures have the potential to track the sources, fate, and transport of different point and nonpoint pollution sources along streams across different regions.

Longitudinal stream synoptic (LSS) monitoring to evaluate water quality in restored streams.

Impervious surface cover increases peak flows and degrades stream health, contributing to a variety of hydrologic, water quality, and ecological symptoms, collectively known as the urban stream syndrome. Strategies to combat the urban stream syndrome often employ engineering approaches to enhance stream-floodplain reconnection, dissipate erosive forces from urban runoff, and enhance contaminant retention, but it is not always clear how effective such practices are or how to monitor for their effectiveness. In this study, we explore applications of longitudinal stream synoptic (LSS) monitoring (an approach where multiple samples are collected along stream flowpaths across both space and time) to narrow this knowledge gap. Specifically, we investigate (1) whether LSS monitoring can be used to detect changes in water chemistry along longitudinal flowpaths in response to stream-floodplain reconnection and (2) what is the scale over which restoration efforts improve stream quality. We present results for four different classes of water quality constituents (carbon, nutrients, salt ions, and metals) across five watersheds with varying degrees of stream-floodplain reconnection. Our work suggests that LSS monitoring can be used to evaluate stream restoration strategies when implemented at meter to kilometer scales. As streams flow through restoration features, concentrations of nutrients, salts, and metals significantly decline (p < 0.05) or remain unchanged. This same pattern is not evident in unrestored streams, where salt ion concentrations (e.g., Na+, Ca2+, K+) significantly increase with increasing impervious cover. When used in concert with statistical approaches like principal component analysis, we find that LSS monitoring reveals changes in entire chemical mixtures (e.g., salts, metals, and nutrients), not just individual water quality constituents. These chemical mixtures are locally responsive to restoration projects, but can be obscured at the watershed scale and overwhelmed during storm events.

Where the rubber meets the road: Emerging environmental impacts of tire wear particles and their chemical cocktails.

About 3 billion new tires are produced each year and about 800 million tires become waste annually. Global dependence upon tires produced from natural rubber and petroleum-based compounds represents a persistent and complex environmental problem with only partial and often-times, ineffective solutions. Tire emissions may be in the form of whole tires, tire particles, and chemical compounds, each of which is transported through various atmospheric, terrestrial, and aquatic routes in the natural and built environments. Production and use of tires generates multiple heavy metals, plastics, PAH's, and other compounds that can be toxic alone or as chemical cocktails. Used tires require storage space, are energy intensive to recycle, and generally have few post-wear uses that are not also potential sources of pollutants (e.g., crumb rubber, pavements, burning). Tire particles emitted during use are a major component of microplastics in urban runoff and a source of unique and highly potent toxic substances. Thus, tires represent a ubiquitous and complex pollutant that requires a comprehensive examination to develop effective management and remediation. We approach the issue of tire pollution holistically by examining the life cycle of tires across production, emissions, recycling, and disposal. In this paper, we synthesize recent research and data about the environmental and human health risks associated with the production, use, and disposal of tires and discuss gaps in our knowledge about fate and transport, as well as the toxicology of tire particles and chemical leachates. We examine potential management and remediation approaches for addressing exposure risks across the life cycle of tires. We consider tires as pollutants across three levels: tires in their whole state, as particulates, and as a mixture of chemical cocktails. Finally, we discuss information gaps in our understanding of tires as a pollutant and outline key questions to improve our knowledge and ability to manage and remediate tire pollution.

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.

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.

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.

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.

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.

Long-term assessment of floodplain reconnection as a stream restoration approach for managing nitrogen in ground and surface waters.

Stream restoration is a popular approach for managing nitrogen (N) in degraded, flashy urban streams. Here, we investigated the long-term effects of stream restoration involving floodplain reconnection on riparian and in-stream N transport and transformation in an urban stream in the Chesapeake Bay watershed. We examined relationships between hydrology, chemistry, and biology using a Before/After-Control/Impact (BACI) study design to determine how hydrologic flashiness, nitrate (NO3 -) concentrations (mg/L), and N flux, both NO3 - and total N (kg/yr), changed after the restoration and floodplain hydrologic reconnection to its stream channel. We examined two independent surface water and groundwater data sets (EPA and USGS) collected from 2002-2012 at our study sites in the Minebank Run watershed. Restoration was completed during 2004 and 2005. Afterward, the monthly hydrologic flashiness index, based on mean monthly discharge, decreased over time from 2002 and 2008. However, from 2008-2012 hydrologic flashiness returned to pre-restoration levels. Based on the EPA data set, NO3 - concentration in groundwater and surface water was significantly less after restoration while the control site showed no change. DOC and NO3 - were negatively related before and after restoration suggesting C limitation of N transformations. Long-term trends in surface water NO3 - concentrations based on USGS surface water data showed downward trends after restoration at both the restored and control sites, whereas specific conductance showed no trend. Comparisons of NO3 - concentrations with Cl- concentrations and specific conductance in both ground and surface waters suggested that NO3 - reduction after restoration was not due to dilution or load reductions from the watershed. Modeled NO3 - flux decreased post restoration over time but the rate of decrease was reduced likely due to failure of restoration features that facilitated N transformations. Groundwater NO3 - concentrations varied among stream features suggesting that some engineered features may be functionally better at creating optimal conditions for N retention. However, some engineered features eroded and failed post restoration thereby reducing efficacy of the stream restoration to reduce flashiness and NO3 - flux. N management via stream restoration will be most effective where flashiness can be reduced and DOC made available for denitrifiers. Stream restoration may be an important component of holistic watershed management including stormwater management and nutrient source control if stream restoration and floodplain reconnection can be done in a manner to resist the erosive effects of large storm events that can degrade streams to pre-restoration conditions. Long-term evolution of water quality functions in response to degradation of restored stream channels and floodplains from urban stressors and storms over time warrants further study, however.

Shifting stoichiometry: Long-term trends in stream-dissolved organic matter reveal altered C:N ratios due to history of atmospheric acid deposition.

Dissolved organic carbon (DOC) and nitrogen (DON) are important energy and nutrient sources for aquatic ecosystems. In many northern temperate, freshwater systems DOC has increased in the past 50 years. Less is known about how changes in DOC may vary across latitudes, and whether changes in DON track those of DOC. Here, we present long-term DOC and DON data from 74 streams distributed across seven sites in biomes ranging from the tropics to northern boreal forests with varying histories of atmospheric acid deposition. For each stream, we examined the temporal trends of DOC and DON concentrations and DOC:DON molar ratios. While some sites displayed consistent positive or negative trends in stream DOC and DON concentrations, changes in direction or magnitude were inconsistent at regional or local scales. DON trends did not always track those of DOC, though DOC:DON ratios increased over time for ~30% of streams. Our results indicate that the dissolved organic matter (DOM) pool is experiencing fundamental changes due to the recovery from atmospheric acid deposition. Changes in DOC:DON stoichiometry point to a shifting energy-nutrient balance in many aquatic ecosystems. Sustained changes in the character of DOM can have major implications for stream metabolism, biogeochemical processes, food webs, and drinking water quality (including disinfection by-products). Understanding regional and global variation in DOC and DON concentrations is important for developing realistic models and watershed management protocols to effectively target mitigation efforts aimed at bringing DOM flux and nutrient enrichment under control.

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.

Optimized suspect screening approach for a comprehensive assessment of the impact of best management practices in reducing micropollutants transport in the Potomac River watershed.

The vast number of chemicals potentially reaching aquatic environment pose a challenge in maintaining the quality of water resources. However, best management practices to improve water quality are typically focused on reducing nutrient transport without assessing how these practices may impact the occurrence of micropollutants. The potential for co-management of nutrients and organic micropollutants exists, but few studies have comprehensively evaluated the suite of contaminants associated with different water quality management practices (riparian zone restoration, stormwater management, etc.). Furthermore, most studies dealing with the determination of micropollutants in environmental samples include only a limited number of target analytes, leaving many contaminants undetected. To address this limitation, there has been a gradual shift in environmental monitoring from using target analysis to either suspect screening analysis (SSA) or non-targeted analysis (NTA), which relies on accurate mass measurements, mass spectral fragmentation patterns, and retention time information obtained using liquid chromatography coupled to high-resolution mass spectrometry. The work presented in this paper focuses on a wide-scope detection of micropollutants in surface water samples from the Potomac River watershed (United States). An in-house database composed of 1039 compounds based on experimental analysis of primary standards was established, and SSA workflow was optimized and applied to determine the presence of micropollutants in surface water. A total of 103 micropollutants were detected in the samples, some of which are contaminants that were not previously monitored and belong to various classes such as pharmaceuticals, personal care products, per-and polyfluoroalkyl substances and other persistent industrial chemicals. The impact of best management practices being implemented for nitrogen and phosphorus reductions were also assessed for their potential to reduce micropollutant transport. This work illustrates the advantages of suspect screening methods to determine a large number of micropollutants in environmental samples and reveals the potential to co-manage a diverse array of micropollutants based on shared transport and transformation mechanisms in watersheds.

Evidence that watershed nutrient management practices effectively reduce estrogens in environmental waters.

We evaluate the impacts of different nutrient management strategies on the potential for co-managing estrogens and nutrients in environmental waters of the Potomac watershed of the Chesapeake Bay. These potential co-management approaches represent agricultural and urban runoff, wastewater treatment plant effluent, and combined sewer overflow replacements. Twelve estrogenic compounds and their metabolites were analysed by gas chromatography-mass spectrometry. Estrogenic activity (E2Eq) was measured by in vitro bioassay. We detected estrone E1 (0.05-6.97 ng L-1) and estriol E3 (below detection-8.13 ng L-1) and one conjugated estrogen (estrone-3-sulfate E1-3S; below detection-8.13 ng L-1). E1 was widely distributed and positively correlated with E2Eq, water temperature, and dissolved organic carbon (DOC). Among nonpoint sources, E2Eq, and concentrations of E1, soluble reactive phosphorus (SRP) and total dissolved nitrogen (TDN) decreased by 51-61%, 77-82%, 62-64%, 4-16% in restored urban and agricultural streams with best management practices (BMPs) relative to unrestored streams without BMPs. In a wastewater treatment plant (Blue Plains WWTP), >94% of E1, E1-3S, E3, E2Eq and TDN were removed while SRP increased by 305% during nitrification/denitrification as a part of advanced wastewater treatment. Consequently, E1 and TDN concentrations in WWTP effluents were comparable or even lower than those observed in the receiving stream or river waters, and the effects of wastewater discharges on downstream E1 and TDN concentrations were minor. Highest E2Eq value and concentrations of E1, E3, and TDN were detected in combined sewer overflow (CSO). This study suggests that WWTP upgrades with biological nutrient removal, CSO management, and certain agricultural and urban BMPs for nutrient controls have the potential to remove estrogens from point and nonpoint sources along with other contaminants in streams and rivers.

Theoretical Perspectives of the Baltimore Ecosystem Study: Conceptual Evolution in a Social-Ecological Research Project.

The Earth's population will become more than 80% urban during this century. This threshold is often regarded as sufficient justification for pursuing urban ecology. However, pursuit has primarily focused on building empirical richness, and urban ecology theory is rarely discussed. The Baltimore Ecosystem Study (BES) has been grounded in theory since its inception and its two decades of data collection have stimulated progress toward comprehensive urban theory. Emerging urban ecology theory integrates biology, physical sciences, social sciences, and urban design, probes interdisciplinary frontiers while being founded on textbook disciplinary theories, and accommodates surprising empirical results. Theoretical growth in urban ecology has relied on refined frameworks, increased disciplinary scope, and longevity of interdisciplinary interactions. We describe the theories used by BES initially, and trace ongoing theoretical development that increasingly reflects the hybrid biological-physical-social nature of the Baltimore ecosystem. The specific mix of theories used in Baltimore likely will require modification when applied to other urban areas, but the developmental process, and the key results, will continue to benefit other urban social-ecological research projects.

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.

Seeing the light: urban stream restoration affects stream metabolism and nitrate uptake via changes in canopy cover.

The continually increasing global population residing in urban landscapes impacts numerous ecosystem functions and services provided by urban streams. Urban stream restoration is often employed to offset these impacts and conserve or enhance the various functions and services these streams provide. Despite the assumption that "if you build it, [the function] will come," current understanding of the effects of urban stream restoration on stream ecosystem functions are based on short term studies that may not capture variation in restoration effectiveness over time. We quantified the impact of stream restoration on nutrient and energy dynamics of urban streams by studying 10 urban stream reaches (five restored, five unrestored) in the Baltimore, Maryland, USA, region over a two-year period. We measured gross primary production (GPP) and ecosystem respiration (ER) at the whole-stream scale continuously throughout the study and nitrate (NO3- -N) spiraling rates seasonally (spring, summer, autumn) across all reaches. There was no significant restoration effect on NO3- -N spiraling across reaches. However, there was a significant canopy cover effect on NO3- -N spiraling, and directly comparing paired sets of unrestored-restored reaches showed that restoration does affect NO3- -N spiraling after accounting for other environmental variation. Furthermore, there was a change in GPP : ER seasonality, with restored and open-canopied reaches exhibiting higher GPP : ER during summer. The restoration effect, though, appears contingent upon altered canopy cover, which is likely to be a temporary effect of restoration and is a driver of multiple ecosystem services, e.g., habitat, riparian nutrient processing. Our results suggest that decision-making about stream restoration, including evaluations of nutrient benefits, clearly needs to consider spatial and temporal dynamics of canopy cover and trade-offs among multiple ecosystem services.

Regenerative stormwater conveyance (RSC) for reducing nutrients in urban stormwater runoff depends upon carbon quantity and quality.

Regenerative stormwater conveyance (RSC), a relatively new stormwater management approach, is extensively implemented throughout the mid-Atlantic for nutrient control, but little is known of its pollutant reduction capabilities and controlling factors. This study examined effects of organic carbon (C) quantity and quality on stream water quality and nutrient retention at two RSCs near Annapolis, Maryland, USA by comparing longitudinal changes in water quality at paired restored and unrestored stream reaches, and conducting lab experiments simulating RSC processes. Results showed that RSCs consistently had lower dissolved oxygen saturation (DO%) and pH relative to nearby unrestored streams, probably due to release of labile dissolved organic carbon (DOC). At one RSC, with high nitrate (NO3-) inputs, retention of N (16-37%) and release of DOC (18-54%) were observed with the highest retention of N during summer, and the rates of N retention and DOC release were larger than that of the adjacent unrestored tributary (N: 5-8%, DOC: <18%). At another RSC site with lower NO3- concentrations, N retention and DOC release were not apparent. Mesocosm experiments showed that NO3- retention varies with organic C quantity and quality depending on incubating temperature; retention of total N did not increase with organic C due to release of other N species (e.g., organic N). Lab mesocosms showed an increase in the release of soluble reactive phosphorus (SRP) with increasing organic C quantity and quality. However, field measurements did not show any evidence of SRP release at RSCs. The changes in SRP concentrations in streams seemed to be a function of iron levels and leaf litter inputs, but control factors for SRP warrant further investigation. This study suggests that RSC as a restoration approach may be effective for reducing N depending upon C quantity and quality as well as water temperature and N levels.