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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.

Freshwater salinization is an emerging global problem impacting safe drinking water, ecosystem health and biodiversity, infrastructure corrosion, and food production. Freshwater salinization originates from diverse anthropogenic and geologic sources including road salts, human-accelerated weathering, sewage, urban construction, fertilizer, mine drainage, resource extraction, water softeners, saltwater intrusion, and evaporative concentration of ions due to hydrologic alterations and climate change. The complex interrelationships between salt ions and chemical, biological, and geologic parameters and consequences on the natural, social, and built environment are called Freshwater Salinization Syndrome (FSS). Here, we provide a comprehensive overview of salinization issues (past, present, and future), and we investigate drivers and solutions. We analyze the expanding global magnitude and scope of FSS including its discovery in humid regions, connections to human-accelerated weathering and mobilization of ‘chemical cocktails.’ We also present data illustrating: (1) increasing trends in salt ion concentrations in some of the world’s major freshwaters, including critical drinking water supplies; (2) decreasing trends in nutrient concentrations in rivers due to regulations but increasing trends in salinization, which have been due to lack of adequate management and regulations; (3) regional trends in atmospheric deposition of salt ions and storage of salt ions in soils and groundwater, and (4) applications of specific conductance as a proxy for tracking sources and concentrations of groups of elements in freshwaters. We prioritize FSS research needs related to better understanding: (1) effects of saltwater intrusion on ecosystem processes, (2) potential health risks from groundwater contamination of home wells, (3) potential risks to clean and safe drinking water sources, (4) economic and safety impacts of infrastructure corrosion, (5) alteration of biodiversity and ecosystem functions, and (6) application of high-frequency sensors in state-of-the art monitoring and management. We evaluate management solutions using a watershed approach spanning air, land, and water to explore variations in sources, fate and transport of different salt ions (e.g. monitoring of atmospheric deposition of ions, stormwater management, groundwater remediation, and managing road runoff). We also identify tradeoffs in management approaches such as unanticipated retention and release of chemical cocktails from urban stormwater management best management practices (BMPs) and unintended consequences of alternative deicers on water quality. Overall, we show that FSS has direct and indirect effects on mobilization of diverse chemical cocktails of ions, metals, nutrients, organics, and radionuclides in freshwaters with mounting impacts. Our comprehensive review suggests what could happen if FSS were not managed into the future and evaluates strategies for reducing increasing risks to clean and safe drinking water, human health, costly infrastructure, biodiversity, and critical ecosystem services.

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.

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.

1. Urban streams are degraded by a suite of factors, including burial beneath urban infrastructure, such as roads or parking lots, which eliminates light and reduces direct organic matter inputs to streams from riparian zones. These changes to stream metabolism and terrestrial carbon contribution will likely have consequences for organic matter metabolism by microbes and dissolved organic matter (DOM) use patterns in streams. Respiration by heterotrophic biofilms drives the nitrogen and phosphorus cycles, but we lack a clear understanding of how stream burial and seasonality affect microbial carbon use. 2. We studied seasonal changes (autumn, spring, and summer) in organic matter metabolism by microbial communities in open and buried reaches of three urban streams in Cincinnati, OH. We characterised DOM quality using fluorescence spectroscopy and extracellular enzyme profiles, and we measured the respiration response to carbon supplements in nutrient diffusing substrata (NDS). We hypothesised: (1) that algal production would lead to higher quality DOM in spring compared to other seasons and in open compared to buried reaches, (2) lower reliance of microbial respiration on recalcitrant carbon sources in spring and in open reaches, and (3) that microbial respiration would increase in response to added carbon in autumn and in buried reaches. 3. Several fluorescence metrics showed higher quality DOM in spring than autumn, but only the metric of recalcitrant humic compounds varied by reach, with more humic DOM in open compared to buried reaches. This likely reflected open reaches as an avenue for direct terrestrial inputs from the riparian zone. 4. Extracellular enzyme assays showed that microbes in buried reaches allocated more effort to degrade recalcitrant carbon sources, consistent with a lack of labile carbon compounds due to limited photosynthesis. Nitrogen acquisition enzymes were highest in autumn coincident with riparian leaf inputs to the streams. Buried and open reaches both responded more strongly to added carbon in autumn when terrestrial leaf inputs dominated compared to the spring when vernal algal blooms were pronounced. 5. Our data show that stream burial affects the quality of the DOM pool with consequences for how microbes use those carbon sources, and that heterotrophic respiration increased on carbon-supplemented NDS in buried and open stream reaches in both seasons. Different carbon quality and use patterns suggest that urban stream infrastructure affects spatiotemporal patterns of bacterial respiration, with likely consequences for nitrogen and/or phosphorus cycling given that carbon use drives other biogeochemical cycles. Management actions that increase light to buried streams could shift the balance between allochthonous and autochthonous DOM in urban streams with consequences for spatiotemporal patterns in bacterial metabolism.

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

Inland freshwater salinity is rising worldwide, a phenomenon called the freshwater salinization syndrome (FSS). We investigate a potential conflict between managing the FSS and indirect potable reuse, the practice of augmenting water supplies through the addition of highly treated wastewater (reclaimed water) to surface waters and groundwaters. From time-series data collected over 25 years, we quantify the contributions of three salinity sources—a water reclamation facility and two rapidly urbanizing watersheds—to the rising concentration of sodium (a major ion associated with the FSS) in a regionally important drinking-water reservoir in the Mid-Atlantic United States. Sodium mass loading to the reservoir is primarily from watershed runoff during wet weather and reclaimed water during dry weather. Across all timescales evaluated, sodium concentration in the reclaimed water is higher than in outflow from the two watersheds. Sodium in reclaimed water originates from chemicals added during wastewater treatment, industrial and commercial discharges, human excretion and down-drain disposal of drinking water and sodium-rich household products. Thus, numerous opportunities exist to reduce the contribution of indirect potable reuse to sodium pollution at this site, and the FSS more generally. These efforts will require deliberative engagement with a diverse community of watershed stakeholders and careful consideration of the local political, social and environmental context. Freshwater salinization syndrome is an emerging threat to freshwater globally. Here the authors quantify the contribution of indirect potable reuse to sodium pollution and suggest a variety of behavioural and technological interventions to address this growing environmental problem.

Este artículo contiene 17 páginas, 6 figuras, 2 tablas., 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 energynutrient 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., National Institute of Food and Agriculture, Grant/Award Number: 1016163, 1019522 and 1022291; Natural Environment Research Council, Grant/Award Number: NE/K010689/1; NSF EPSCoR, Grant/ Award Number: EPS-1929148; Division of Environmental Biology, Grant/ Award Number: 1545288 and 1556603; European Regional Development Fund, Grant/Award Number: RTI2018-094521- B-100 and RYC-2017-22643

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., Highlights • In-house suspect screening database that include 1039 micropollutants was developed • Suspect screening analysis (SSA) workflow was optimized to increase chemical coverage • SSA detected 103 micropollutants in the samples collected from Potomac watershed • BMPs result in co-management of nutrients and micropollutants transport

Understanding transport mechanisms and temporal patterns in the context of metal concentrations in urban streams is important for developing best management practices and restoration strategies to improve water quality. In some cases, in-situ sensors can be used to estimate unknown concentrations of trace metals or to interpolate between sampling events. Continuous sensor data from the United States Geological Survey were analyzed to determine statistically significant relationships between lead, copper, zinc, cadmium, and mercury with turbidity, specific conductance, dissolved oxygen, and discharge for the Hickey Run, Watts Branch, and Rock Creek watersheds in the Washington, D.C. region. We observed a significant negative linear relationship between concentrations of Cu and dissolved oxygen at Rock Creek (p &lt, 0.05). Sometimes, turbidity had significant positive linear relationships with Pb and Hg concentrations. There were negative or positive linear relationships between Pb, Cd, Zn, and Hg and specific conductance. There also appeared to be relationships between watershed areal fluxes of Pb, Cu, Zn, and Cd in streams with turbidity. Watershed monitoring approaches using continuous sensor data have the potential to characterize the frequency, magnitude, and composition of pulses in concentrations and loads of trace metals, which could improve the management and restoration of urban streams.

Urbanized watersheds in colder climates experience episodic salinization due to anthropogenic salt inputs and runoff from impervious surfaces. Episodic salinization can be manifested as a ‘pulse’ in concentrations and fluxes of salt ions lasting from hours to days after snowstorms in response to road salting. Episodic salinization contributes to freshwater salinization syndrome, characterized by cascading mobilization of chemicals and shifting acid–base status. We conducted laboratory experiments and analyzed high-frequency sensor data to investigate the water quality impacts of freshwater salinization syndrome and episodic salinization across 12 watersheds draining two major metropolitan regions along the U.S. East Coast. Sediments from 12 watersheds spanning land use gradients across two metropolitan regions, Baltimore, Maryland and Washington DC, were incubated across a range of replicated salinity treatments (0–10 g/L sodium chloride). There were statistically significant linear increasing trends in calcium and potassium concentrations with experimental salinization across all 12 sites and in magnesium concentrations at 11 of 12 sites (p

Este artículo contiene 25 páginas, 9 figuras., In the Anthropocene, watershed chemical transport is increasingly dominated by novel combinations of 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 corrosion, 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 storms 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., This work was funded by USDA (award # 2016-67019-25280) and NSF-EPSCoR (#1641157) for supporting collaborations at the AGU Chapman Conference on Extreme Climate Events. Significant funding for data collection/analyses in this paper was provided by NSF EAR1521224, NSF CBET1058502, NSF Coastal SEES1426844, NSF DEB-0423476 and DEB-1027188, NSF RI EPSCoR NEWRnet Grant No. IIA-1330406, EPA ORD, Chesapeake Bay Trust, and Multi-state Regional Hatch Project S-1063.

Although many climate predictions suggest that the frequency and intensity of large storm events might increase in the coming decades, few studies document the full impact of such events along their path. Here, we synthesize information on the impact of Hurricane Irene (formed August 21 2011) and Tropical Storm Lee (formed August 30, 2011) on erosion and sediment transport, lake metabolism, riparian hydrology and biogeochemistry, and stream water quality, from North Carolina to Maine. In almost all cases, these storms generated unprecedented changes in water quality (concentrations, loads), from tenfold increases in DOC and 100-fold increases in POC in Maryland, to 100-fold increases in TSS concentrations in Pennsylvania. Overbank flooding and up to 200-year streamflow events were recorded in New York and Vermont. In many cases, particulate loads (e.g. POC, PP, TSS) occurring during Irene and Lee represented more than 30% of the annual load. The dominance of particulate exports over solutes during Irene and Lee is consistent with the mobilization of normally immobile sediment pools, and massive erosion as reported at many locations across the Northeastern US. Several studies reported long lasting (> 1 year) effects of Irene and Lee on cyanobacterial blooms, erosion, or stream suspended sediment concentrations. However, this review also highlighted the lack of a consistent strategy in terms of methods, and measured water quality parameters. This strongly hinders our ability to fully assess the large-scale impact of such events on our environment, and ultimately their impact on our economy and society.

Human-dominated land uses can increase transport of major ions in streams due to the combination of human-accelerated weathering and anthropogenic salts. Calcium, magnesium, sodium, alkalinity, and hardness significantly increased in the drinking water supply for Baltimore, Maryland over almost 50 years (p

Streams and rivers are significant sources of nitrous oxide (N2O), carbon dioxide (CO2), and methane (CH4) globally, and watershed management can alter greenhouse gas (GHG) emissions from streams. We hypothesized that urban infrastructure significantly alters downstream water quality and contributes to variability in GHG saturation and emissions. We measured gas saturation and estimated emission rates in headwaters of two urban stream networks (Red Run and Dead Run) of the Baltimore Ecosystem Study Long-Term Ecological Research project. We identified four combinations of stormwater and sanitary infrastructure present in these watersheds, including: (1) stream burial, (2) inline stormwater wetlands, (3) riparian/floodplain preservation, and (4) septic systems. We selected two first-order catchments in each of these categories and measured GHG concentrations, emissions, and dissolved inorganic and organic carbon (DIC and DOC) and nutrient concentrations biweekly for 1 year. From a water quality perspective, the DOC : NO3− ratio of streamwater was significantly different across infrastructure categories. Multiple linear regressions including DOC : NO3− and other variables (dissolved oxygen, DO; total dissolved nitrogen, TDN; and temperature) explained much of the statistical variation in nitrous oxide (N2O, r2 = 0.78), carbon dioxide (CO2, r2 = 0.78), and methane (CH4, r2 = 0.50) saturation in stream water. We measured N2O saturation ratios, which were among the highest reported in the literature for streams, ranging from 1.1 to 47 across all sites and dates. N2O saturation ratios were highest in streams draining watersheds with septic systems and strongly correlated with TDN. The CO2 saturation ratio was highly correlated with the N2O saturation ratio across all sites and dates, and the CO2 saturation ratio ranged from 1.1 to 73. CH4 was always supersaturated, with saturation ratios ranging from 3.0 to 2157. Longitudinal surveys extending form headwaters to third-order outlets of Red Run and Dead Run took place in spring and fall. Linear regressions of these data yielded significant negative relationships between each gas with increasing watershed size as well as consistent relationships between solutes (TDN or DOC, and DOC : TDN ratio) and gas saturation. Despite a decline in gas saturation between the headwaters and stream outlet, streams remained saturated with GHGs throughout the drainage network, suggesting that urban streams are continuous sources of CO2, CH4, and N2O. Our results suggest that infrastructure decisions can have significant effects on downstream water quality and greenhouse gases, and watershed management strategies may need to consider coupled impacts on urban water and air quality.

Increasing trends in base cations, pH, and salinity of freshwaters have been documented in US 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. R 2 = 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 showed co-mobilization (i.e. correlations among combinations of specific conductance (SC), 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 h after SC peaked, suggesting ongoing cation exchange in soils and stream sediments. Mn and Cu concentrations predicted from SC 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 SC 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.

Urbanization has altered the fate and transport of anthropogenic nitrogen (N) in rivers and estuaries globally. This study evaluates the capacity of an urbanizing river–estuarine continuum to transform N inputs from the world's largest advanced (e.g., phosphorus and biological N removal) wastewater treatment facility. Effluent samples and surface water were collected monthly along the Potomac River estuary from Washington D.C. to the Chesapeake Bay over a distance of 150 km. In conjunction with box model mass balances, nitrate stable isotopes and mixing models were used to trace the fate of urban wastewater nitrate. Nitrate concentrations and δ15N-NO3− values were higher down-estuary from the Blue Plains wastewater outfall in Washington D.C. (2.25 ± 0.62 mg L−1 and 25.7 ± 2.9 ‰, respectively) compared to upper-estuary concentrations (1.0 ± 0.2 mg L−1 and 9.3 ± 1.4 ‰, respectively). Nitrate concentration then decreased rapidly within 30 km down-estuary (to 0.8 ± 0.2 mg L−1), corresponding to an increase in organic nitrogen and dissolved organic carbon, suggesting biotic uptake and organic transformation. TN loads declined down-estuary (from an annual average of 48 000 ± 5000 kg day−1 at the sewage treatment plant outfall to 23 000 ± 13 000 kg day−1 at the estuary mouth), with the greatest percentage decrease during summer and fall. Annually, there was a 70 ± 31 % loss in wastewater NO3− along the estuary, and 28 ± 6 % of urban wastewater TN inputs were exported to the Chesapeake Bay, with the greatest contribution of wastewater TN loads during the spring. Our results suggest that biological transformations along the urban river–estuary continuum can significantly transform wastewater N inputs from major cities globally, and more work is necessary to evaluate the potential of organic nitrogen and carbon to contribute to eutrophication and hypoxia.

Este artículo contiene 19 páginas, 3 tablas, 6 figuras., River networks modify material transfer from land to ocean. Understanding the factors regulating this function for different gaseous, dissolved, and particulate constituents is critical to quantify the local and global effects of climate and land use change. We propose the River Network Saturation (RNS) concept as a generalization of how river network regulation of material fluxes declines with increasing flows due to imbalances between supply and demand at network scales. River networks have a tendency to become saturated (supply demand) under higher flow conditions because supplies increase faster than sink processes. However, the flow thresholds under which saturation occurs depends on a variety of factors, including the inherent process rate for a given constituent and the abundance of lentic waters such as lakes, ponds, reservoirs, and fluvial wetlands within the river network. As supply increases, saturation at network scales is initially limited by previously unmet demand in downstream aquatic ecosystems. The RNS concept describes a general tendency of river network function that can be used to compare the fate of different constituents among river networks. New approaches using nested in situ high-frequency sensors and spatially extensive synoptic techniques offer the potential to test the RNS concept in different settings. Better understanding of when and where river networks saturate for different constituents will allow for the extrapolation of aquatic function to broader spatial scales and therefore provide information on the influence of river function on continental element cycles and help identify policy priorities., This paper is a product of the AGU Chapman Conference on Extreme Climate Events held in San Juan Puerto Rico in January 2017. We would like to thank the USDA (award # 2016-67019-25280), NSF-EPSCoR (#1641157), USGS, National CZO office, and the US Forest Service IITF for funding this AGU Chapman conference on Extreme Climate and providing travel funds to the attendees. This research was also supported by National Science Foundation (NSF) Macrosystem Biology (EF-1065286), NSF EPSCoR (EPS-1101245), and NSF LTER to Plum Island Ecosystem (OCE-1238212 and 1637630). Partial funding was provided by the New Hampshire Agricultural Experiment Station, USDA National Institute of Food and Agriculture Hatch Project NH00609, and is Scientific Contribution #2743.

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.

An improved understanding of sources and timing of water, carbon, and nutrient fluxes associated with urban infrastructure and stream restoration is critical for guiding effective watershed management globally. We investigated how sources, fluxes, and flowpaths of water, carbon (C), nitrogen (N), and phosphorus (P) shift in response to differences in urban stream restoration and sewer infrastructure. We compared an urban restored stream with two urban degraded streams draining varying levels of urban development and one stream with upland stormwater management systems over a 3-year period. We found that there was significantly decreased peak discharge in response to precipitation events following stream restoration. Similarly, we found that the restored stream showed significantly lower (p −1) compared with two urban degraded streams (ranging from 44.9 ± 4.5 to 55.4 ± 5.8 mm day−1) draining higher impervious surface cover, and the stream-draining stormwater management systems and less impervious surface cover in its watershed (13.2 ± 1.9 mm day−1). The restored stream exported most carbon, nitrogen, and phosphorus at relatively lower streamflow than the two more urban catchments, which exported most carbon and nutrients at higher streamflow. Annual exports of total carbon (6.6 ± 0.5 kg ha−1 yr−1), total nitrogen (4.5 ± 0.3 kg ha−1 yr−1), and total phosphorus (161 ± 15 kg ha−1 yr−1) were significantly lower in the restored stream compared to both urban degraded streams (p

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 (NO(3)(−)) 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

There has been increased salinization of fresh water over decades due to the use of road salt deicers, wastewater discharges, saltwater intrusion, human-accelerated weathering, and groundwater irrigation. Salinization can mobilize bioreactive elements (carbon, nitrogen, phosphorus, sulfur) chemically via ion exchange and/or biologically via influencing of microbial activity. However, the effects of salinization on coupled biogeochemical cycles are still not well understood. We investigated potential impacts of increased salinization on fluxes of bioreactive elements from stream ecosystems (sediments and riparian soils) to overlying stream water and evaluated the implications of percent urban land use on salinization effects. Two-day incubations of sediments and soils with stream and deionized water across three salt levels were conducted at eight routine monitoring stations across a land-use gradient at the Baltimore Ecosystem Study Long-Term Ecological Research (LTER) site in the Chesapeake Bay watershed. Results indicated (1) salinization typically increased sediment releases of labile dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), total dissolved Kjeldahl nitrogen (TKN) (ammonium + ammonia + dissolved organic nitrogen), and sediment transformations of nitrate; (2) salinization generally decreased DOC aromaticity and fluxes of soluble reactive phosphorus from both sediments and soils; (3) the effects of increased salinization on sediment releases of DOC and TKN and DOC quality increased with percentage watershed urbanization. Biogeochemical responses to salinization varied between sediments and riparian soils in releases of DOC and DIC, and nitrate transformations. The differential responses of riparian soils and sediments to increased salinization were likely due to differences in organic matter sources and composition. Our results suggest that short-term increases in salinization can cause releases of significant amounts of labile organic carbon and nitrogen from stream substrates and organic transformations of nitrogen and phosphorus in urban watersheds. Given that salinization of fresh water will increase in the future due to human activities, significant impacts on carbon and nutrient mobilization and water quality should be anticipated.

Rivers transport and transform significant quantities of carbon to coastal zones globally. Urbanization and climate change impact the transport and transformation of carbon by altering hydrology, water temperatures, and in-stream metabolism rates. Changes in exports, sources, and metabolism of carbon influence ecosystem processes, food webs, and greenhouse gases. We characterized exports, sources, and metabolism of carbon in four urban watersheds using a combination of discrete stream chemistry measurements and continuous water-quality sensors. Over three years, watershed DOC exports in the Baltimore-Washington D.C. metropolitan area ranged from 9 to 23 kg ha−1 year−1. DIC exports ranged from 19 to 59 kg ha−1 year−1. Daily contributions from in-stream metabolism varied between −65 and 90 % of DIC export depending on stream size and streamflow conditions. Negative contributions from metabolism occurred on days when streams were autotrophic. All streams were heterotrophic during 60 to 87 % of each year, but showed significant peaks in autotrophy during spring and summer. Differences in the timing and magnitude of peaks in springtime net ecosystem productivity were likely driven by varying light availability across streams of different sizes and riparian shading. CO2 was consistently over-saturated with respect to the atmosphere on all sampling dates and was 0.25–2.9 mg C L−1. Exports, sources, and metabolism of DOC and DIC showed strong predictable patterns across streamflow. Thus, we present a new conceptual model for predicting carbon transport and transformation across changing streamflow and light availability (with impacts on sources and fluxes of DOC, DIC, and CO2). Overall, our results and conceptual model suggest that urbanization accelerates the transition of streams from transporters to transformers of carbon across streamflow, with implications for timing and magnitude of CO2 fluxes, river alkalinization, and oxygen demand in downstream waters.

We calculated watershed nitrogen (N) retention (inputs–outputs)/inputs) each year from 1999–2013 for nine sub-watersheds along an urban–rural gradient near Baltimore MD to determine how land use and climate influence watershed N flux. Retention is critical to efforts to control coastal eutrophication through regulatory efforts that mandate reductions in the total maximum daily load (TMDL) of N that specific water bodies can receive. Retention decreased with urbanization as well as with increases in precipitation with retention decreasing from an average of 91% in the forested sub-watershed to 16% in the most urban sub-watershed. Export was 23% higher, and retention was 7% lower in winter (November–April) than during the growing season. Total N delivery to Baltimore Harbor varied almost threefold between wet and dry years, which is significant relative to the total annual export allowed for all non-point sources to the harbor under the TMDL. These results suggest that expectations for TMDLs should consider watershed land use and climate variability, and their potential for change if they are to result in improvements in receiving water quality.

The structure, function, and services of urban ecosystems evolve over time scales from seconds to centuries as Earth’s population grows, infrastructure ages, and sociopolitical values alter them. In order to systematically study changes over time, the concept of “urban evolution” was proposed. It allows urban planning, management, and restoration to move beyond reactive management to predictive management based on past observations of consistent patterns. Here, we define and review a glossary of core concepts for studying urban evolution, which includes the mechanisms of urban selective pressure and urban adaptation. Urban selective pressure is an environmental or societal driver contributing to urban adaptation. Urban adaptation is the sequential process by which an urban structure, function, or services becomes more fitted to its changing environment or human choices. The role of water is vital to driving urban evolution as demonstrated by historical changes in drainage, sewage flows, hydrologic pulses, and long-term chemistry. In the current paper, we show how hydrologic traits evolve across successive generations of urban ecosystems via shifts in selective pressures and adaptations over time. We explore multiple empirical examples including evolving: (1) urban drainage from stream burial to stormwater management; (2) sewage flows and water quality in response to wastewater treatment; (3) amplification of hydrologic pulses due to the interaction between urbanization and climate variability; and (4) salinization and alkalinization of fresh water due to human inputs and accelerated weathering. Finally, we propose a new conceptual model for the evolution of urban waters from the Industrial Revolution to the present day based on empirical trends and historical information. Ultimately, we propose that water itself is a critical driver of urban evolution that forces urban adaptation, which transforms the structure, function, and services of urban landscapes, waterways, and civilizations over time.

Significance Salinization and alkalinization impact water quality, but these processes have been studied separately, except in arid regions. Globally, salinization has been largely attributed to agriculture, resource extraction, and land clearing. Alkalinization has been attributed to recovery from acidification, with less recognition as an environmental issue. We show that salinization and alkalinization are linked, and trends in these processes impact most of the drainage area of the United States. Increases in salinity and alkalinity are caused by inputs of salts containing strong bases and carbonates that originate from anthropogenic sources and accelerated weathering. We develop a conceptual model unifying our understanding of salinization and alkalinization and its drivers and impacts on fresh water in North America over the past century., Salt pollution and human-accelerated weathering are shifting the chemical composition of major ions in fresh water and increasing salinization and alkalinization across North America. We propose a concept, the freshwater salinization syndrome, which links salinization and alkalinization processes. This syndrome manifests as concurrent trends in specific conductance, pH, alkalinity, and base cations. Although individual trends can vary in strength, changes in salinization and alkalinization have affected 37% and 90%, respectively, of the drainage area of the contiguous United States over the past century. Across 232 United States Geological Survey (USGS) monitoring sites, 66% of stream and river sites showed a statistical increase in pH, which often began decades before acid rain regulations. The syndrome is most prominent in the densely populated eastern and midwestern United States, where salinity and alkalinity have increased most rapidly. The syndrome is caused by salt pollution (e.g., road deicers, irrigation runoff, sewage, potash), accelerated weathering and soil cation exchange, mining and resource extraction, and the presence of easily weathered minerals used in agriculture (lime) and urbanization (concrete). Increasing salts with strong bases and carbonates elevate acid neutralizing capacity and pH, and increasing sodium from salt pollution eventually displaces base cations on soil exchange sites, which further increases pH and alkalinization. Symptoms of the syndrome can include: infrastructure corrosion, contaminant mobilization, and variations in coastal ocean acidification caused by increasingly alkaline river inputs. Unless regulated and managed, the freshwater salinization syndrome can have significant impacts on ecosystem services such as safe drinking water, contaminant retention, and biodiversity.

Further information on study site characteristics and results from analysis of long-term trends and sensor data.

Este artículo contiene 7 páginas, 3 figuras., We synthesize and summarize main findings from a special issue examining the origins, evolution, and resilience of diverse water quality responses to extreme climate events resulting from a Chapman Conference of the American Geophysical Union (AGU). Origins refer to sequences of interactive disturbances and antecedent conditions that influence diversification of water quality responses to extreme events. Evolution refers to the amplification, intensification, and persistence of water quality signals across space and time in watersheds. Resilience refers to strategies for managing and minimizing extreme water quality impacts and ecosystem recovery. The contributions of this special issue, taken together, highlight the following: (1) there is diversification in the origins of water quality responses to extreme climate events based on the intensity, duration, and magnitude of the event mediated by previous historical conditions; (2) interactions between climate variability and watershed disturbances (e.g., channelization of river networks, land use change, and deforestation) amplify water quality ‘pulses,’ which can manifest as large changes in chemical concentrations and fluxes over relatively short time periods. In the context of the evolution of water quality responses, results highlight: (3) there are high intensity and long-term climate events, which can generate unique sequences in water quality, which have differential impacts on persistence of water quality problems and ecosystem recovery rates; and (4) ‘chemical cocktails’ or novel mixtures of elements and compounds are transported and transformed during extreme climate events. The main findings regarding resilience to extreme climate events are that: (5) river restoration strategies for reducing pollution from extreme events can be improved by preserving and restoring floodplains, wetlands, and oxbow ponds, which enhance hydrologic and biogeochemical retention, and lengthen the distribution of hydrologic residence times; and (6) the biogeochemical capacity for stream and river ecosystems to retain and transform pollution from landscapes can become ‘‘saturated’’ during floods unless watershed pollution sources are reduced. Finally, the unpredictable occurrence of extreme climate events argues for wider deployment of high-frequency, in situ sensors for monitoring, managing, and modeling diverse water quality responses. These sensors can be used to develop robust proxies for chemical cocktails, detect water quality violations following extreme climate events, and effectively trace the trajectory of water quality recovery in response to managing ecosystem resilience.

Land use and climate change can accelerate the depletion of freshwater resources that support humans and ecosystem services on a global scale. Here, we briefly review studies from around the world, and highlight those in this special issue. We identify stages that characterize increasing interaction between land use and climate change. During the first stage, hydrologic modifications and the built environment amplify overland flow via processes associated with runoff-dominated ecosystems (e.g., soil compaction, impervious surface cover, drainage, and channelization). During the second stage, changes in water storage impact the capacity of ecosystems to buffer extremes in water quantity and quality (e.g., either losses in snowpack, wetlands, and groundwater recharge or gains in water and nutrient storage behind dams in reservoirs). During the third stage, extremes in water quantity and quality contribute to losses in ecosystem services and water security (e.g., clean drinking water, flood mitigation, and habitat availability). During the final stage, management and restoration strategies attempt to regain lost ecosystem structure, function, and services but need to adapt to climate change. By anticipating the increasing interaction between land use and climate change, intervention points can be identified, and management strategies can be adjusted to improve outcomes for realistic expectations. Overall, global water security cannot be adequately restored without considering an increasing interaction between land use and climate change across progressive stages and our ever-increasing human domination of the water cycle from degradation to ecosystem restoration.

Urban streams are exposed to multiple different stressors on a regular basis, with increased hydrological flashiness representing a common urban stream stressor. Stream metabolism, the coupled ecosystem functions of gross primary production (GPP) and ecosystem respiration (ER), controls numerous other ecosystem functions and integrates multiple processes occurring within streams. We examined the effect of one large (Superstorm Sandy) and multiple small and moderately sized flood events in Baltimore, Maryland, to quantify the response and recovery of urban stream GPP and ER before and after floods of different magnitudes. We also compared GPP and ER before and after Superstorm Sandy to literature values. We found that both GPP and ER decreased dramatically immediately following floods of varying magnitudes, but on average GPP was more reduced than ER (80% and 66% average reduction in GPP and ER, respectively). Both GPP and ER recovered rapidly following floods within 4–18 d, and recovery intervals did not differ significantly between GPP and ER. During the two‐week recovery following Superstorm Sandy, two urban streams exhibited a range of metabolic activity equivalent to ~15% of the entire range of GPP and ER reported in a recent meta‐analysis of stream metabolism. Urban streams exhibit a substantial proportion of the natural variation in metabolism found across stream ecosystems over relatively short time scales. Not only does urbanization cause increased hydrological flashiness, it appears that metabolic activity in urban streams may be less resistant, but also more resilient to floods than in other streams draining undeveloped watersheds, which have been more studied. Our results show that antecedent conditions must be accounted for when drawing conclusions about stream metabolism measurements, and the rapid recovery and resilience of urban streams should be considered in watershed management and stream restoration strategies targeting ecosystem functions and services.

This overview and synthesis paper focuses on the evolution of urban biogeochemical cycles across time. We synthesize empirical data and review existing literature, including papers in this special issue, and we propose the concept of “urban evolution.” The built environment often changes quickly in response to human activities, thus contributing to an urban evolution that affects structure, function, and ecosystem services of human settlements over time. Depending upon management, these changes can result in rapid losses of ecosystem functions/services or progress towards restoration. We explore urban evolution through empirical examples such as: (1) land development and nitrogen inputs within a metropolitan region over half a century; (2) watershed drainage by different forms of stormwater management over decades; (3) human-accelerated weathering in urbanized watersheds over decades; and (4) global salinization of freshwater across urbanizing landscapes over a century. We also synthesize concepts relevant to studying urban evolution of infrastructure and ecosystems including: (1) urban watersheds have challenged our whole notion of the “watershed approach” due to complex hydrologic boundaries and flow paths over time; (2) the urban hydrologic cycle evolves due to changing infrastructure and human water use over time; (3) the importance of extending research beyond individual sites using an urban watershed approach over space and time; (4) salinization as a universal tracer of watershed urbanization over time; (5) human-accelerated weathering of concrete and construction materials contributing to an “urban karst” over time; (6) human alteration of the carbon cycle in urban watersheds over time; and (7) detecting distinct biogeochemical signatures across cities globally over time. Our synthesis and this special issue suggest that urban biogeochemical cycles have exerted a major influence on the elemental composition of the Earth’s surface from local to global scales. A new global research agenda is needed to track the evolution of urban biogeochemical cycles as land development proceeds and infrastructure/management changes so we can better evaluate potential losses in ecosystem services, set realistic watershed and river restoration goals, and formulate effective environmental policy for Earth’s growing urban population.

Leaf litter plays a critical role in regulating ecological functions in headwater forest streams, whereas the effects of leaves on water quality in urbanized streams are not fully understood. This study examined the potential importance of leaf litter for the release and transformations of organic carbon and nutrients in urban streams, and compared the effects with other types of natural organic substrates (periphyton and stream sediment). Nutrients and organic carbon were leached from senescent leaves of 6 tree species in the laboratory with deionized water, and maximal releases, leaching rate constants, composition and bioavailability of the leached dissolved organic carbon (DOC) were determined. Stream substrates (leaf debris, rocks with periphyton, and sediment) were seasonally collected from urban and forest reference streams of the NSF Baltimore Long-term Ecological Research Site and incubated with overlying stream water to estimate areal fluxes of DOC and nitrogen. Leaf litter leaching showed large ranges in maximal releases of DOC (7.0–131 mg g−1), dissolved organic nitrogen (DON; 0.07–1.39 mg g−1) and total dissolved phosphorus (TDP; 0.14–0.70 mg g−1) among tree species. DOC leaching rate constants, carbon to nitrogen ratios, and DOC bioavailability were all correlated with organic matter quality indicated by fluorescence spectroscopy. Results from substrate incubation experiments showed far higher DOC and DON release and nitrate retention with leaf debris than with sediment, or rocks with periphyton. DOC release from leaf debris was positively correlated with stream nitrate retention at residential and urban sites, with the highest values observed during the fall and lowest during the summer. This study suggests the potential importance of leaf litter quantity and quality on fostering DOC and nutrient release and transformations in urban streams. It also suggests that species-specific impacts of leaves should be considered in riparian buffer and stream restoration strategies.

Restoring urban infrastructure and managing the nitrogen cycle represent emerging challenges for urban water quality. We investigated whether stormwater control measures (SCMs), a form of green infrastructure, integrated into restored and degraded urban stream networks can influence watershed nitrogen loads. We hypothesized that hydrologically connected floodplains and SCMs are “hot spots” for nitrogen removal through denitrification because they have ample organic carbon, low dissolved oxygen levels, and extended hydrologic residence times. We tested this hypothesis by comparing nitrogen retention metrics in two urban stream networks (one restored and one urban degraded) that each contain SCMs, and a forested reference watershed at the Baltimore Long-Term Ecological Research site. We used an urban watershed continuum approach which included sampling over both space and time with a combination of: (1) longitudinal reach-scale mass balances of nitrogen and carbon conducted over 2 years during baseflow and storms (n = 24 sampling dates × 15 stream reaches = 360) and (2) 15N push–pull tracer experiments to measure in situ denitrification in SCMs and floodplain features (n = 72). The SCMs consisted of inline wetlands installed below a storm drain outfall at one urban site (restored Spring Branch) and a wetland/wet pond configured in an oxbow design to receive water during high flow events at another highly urbanized site (Gwynns Run). The SCMs significantly decreased total dissolved nitrogen (TDN) concentrations at both sites and significantly increased dissolved organic carbon concentrations at one site. At Spring Branch, TDN retention estimated by mass balance (g/day) was ~150 times higher within the stream network than the SCMs. There were no significant differences between mean in situ denitrification rates between SCMs and hydrologically connected floodplains. Longitudinal N budgets along the stream network showed that hydrologically connected floodplains were important sites for watershed nitrogen retention due to groundwater–surface water interactions. Overall, our results indicate that hydrologic variability can influence nitrogen source/sink dynamics along engineered stream networks. Our analysis also suggests that some major predictors for watershed N retention were: (1) streamwater and groundwater flux through stream restoration or stormwater management controls, (2) hydrologic residence times, and (3) surface area of hydrologically connected features.

Nonpoint source pollution from agriculture and urbanization is increasing globally at the same time climate extremes have increased in frequency and intensity. We review >200 studies of hydrologic and gaseous fluxes and show how the interaction between land use and climate variability alters magnitude and frequency of carbon, nutrient, and greenhouse gas pulses in watersheds. Agricultural and urban watersheds respond similarly to climate variability due to headwater alteration and loss of ecosystem services to buffer runoff and temperature changes. Organic carbon concentrations/exports increase and organic carbon quality changes with runoff. Nitrogen and phosphorus exports increase during floods (sometimes by an order of magnitude) and decrease during droughts. Relationships between annual runoff and nitrogen and phosphorus exports differ across land use. CH4 and N2O pulses in riparian zones/floodplains predominantly increase with: flooding, warming, low oxygen, nutrient enrichment, and organic carbon. CH4, N2O, and CO2 pulses in streams/rivers increase due to similar factors but effects of floods are less known compared to base flow/droughts. Emerging questions include: (1) What factors influence lag times of contaminant pulses in response to extreme events? (2) What drives resistance/resilience to hydrologic and gaseous pulses? We conclude with eight recommendations for managing watershed pulses in response to interactive effects of land use and climate change.

An urban watershed continuum framework hypothesizes that there are coupled changes in (1) carbon and nitrogen cycling, (2) groundwater-surface water interactions, and (3) ecosystem metabolism along broader hydrologic flowpaths. It expands our understanding of urban streams beyond a reach scale. We evaluated this framework by analyzing longitudinal patterns in: C and N concentrations and mass balances, groundwater-surface interactions, and stream metabolism and carbon quality from headwaters to larger order streams. 52 monitoring sites were sampled seasonally and monthly along the Gwynns Falls watershed, which drains 170 km2 of the Baltimore Long-Term Ecological Research site. Regarding our first hypothesis of coupled C and N cycles, there were significant inverse linear relationships between nitrate and dissolved organic carbon (DOC) and nitrogen longitudinally (P

Urbanization has resulted in the extensive burial and channelization of headwater streams, yet little is known about the impacts of stream burial on ecosystem functions critical for reducing downstream nitrogen (N) and carbon (C) exports. In order to characterize the biogeochemical effects of stream burial on N and C, we measured NO3 − uptake (using 15N-NO3 − isotope tracer releases) and gross primary productivity (GPP) and ecosystem respiration (ER) (using whole stream metabolism measurements). Experiments were carried out during four seasons, in three paired buried and open stream reaches, within the Baltimore Ecosystem Study Long-term Ecological Research site. Stream burial increased NO3 − uptake lengths by a factor of 7.5 (p