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.

Freshwater Salinization Syndrome Alters Nitrogen Transport in Urban Watersheds.

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

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

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

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.

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

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

Human-accelerated weathering increases salinization, major ions, and alkalinization in fresh water across land use.

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<0.05) coinciding with regional urbanization. Across a nearby land use gradient at the Baltimore Long-Term Ecological Research (LTER) site, there were significant increases in concentrations of dissolved inorganic carbon (DIC), Ca2+, Mg2+, Na+, and Si and pH with increasing impervious surfaces in 9 streams monitored bi-weekly over a 3-4 year period (p<0.05). Base cations in urban streams were up to 60 times greater than forest and agricultural streams, and elemental ratios suggested road salt and carbonate weathering from impervious surfaces as potential sources. Laboratory weathering experiments with concrete also indicated that impervious surfaces increased pH and DIC with potential to alkalinize urban waters. Ratios of Na+ and Cl- suggested that there was enhanced ion exchange in the watersheds from road salts, which could mobilize other base cations from soils to streams. There were significant relationships between Ca2+, Mg2+, Na+, and K+ concentrations and Cl-, SO42-, NO3- and DIC across land use (p<0.05), which suggested tight coupling of geochemical cycles. Finally, concentrations of Na+, Ca2+, Mg2+, and pH significantly increased with distance downstream (p<0.05) along a stream network draining 170 km2 of the Baltimore LTER site contributing to river alkalinization. Our results suggest that urbanization may dramatically increase major ions, ionic strength, and pH over decades from headwaters to coastal zones, which can impact integrity of aquatic life, infrastructure, drinking water, and coastal ocean alkalinization.

Longitudinal variability in streamwater chemistry and carbon and nitrogen fluxes in restored and degraded urban stream networks.

Stream restoration has increasingly been used as a best management practice for improving water quality in urbanizing watersheds, yet few data exist to assess restoration effectiveness. This study examined the longitudinal patterns in carbon and nitrogen concentrations and mass balance in two restored (Minebank Run and Spring Branch) and two unrestored (Powder Mill Run and Dead Run) stream networks in Baltimore, Maryland, USA. Longitudinal synoptic sampling showed that there was considerable reach-scale variability in biogeochemistry (e.g., total dissolved nitrogen (TDN), dissolved organic carbon (DOC), cations, pH, oxidation/reduction potential, dissolved oxygen, and temperature). TDN concentrations were typically higher than DOC in restored streams, but the opposite pattern was observed in unrestored streams. Mass balances in restored stream networks showed net uptake of TDN across subreaches (mean ± standard error net uptake rate of TDN across sampling dates for Minebank Run and Spring Branch was 420.3 ± 312.2 and 821.8 ± 570.3 mg m(-2) d(-1), respectively). There was net release of DOC in the restored streams (1344 ± 1063 and 1017 ± 944.5 mg m(-2) d(-1) for Minebank Run and Spring Branch, respectively). Conversely, degraded streams, Powder Mill Run and Dead Run showed mean net release of TDN across sampling dates (629.2 ± 167.5 and 327.1 ± 134.5 mg m(-2) d(-1), respectively) and net uptake of DOC (1642 ± 505.0 and 233.7 ± 125.1 mg m(-2) d(-1), respectively). There can be substantial C and N transformations in stream networks with hydrologically connected floodplain and pond features. Assessment of restoration effectiveness depends strongly on where monitoring is conducted along the stream network. Monitoring beyond the stream-reach scale is recommended for a complete perspective of evaluation of biogeochemical function in restored and degraded urban streams.

Interaction between urbanization and climate variability amplifies watershed nitrate export in Maryland.

We investigated regional effects of urbanization and land use change on nitrate concentrations in approximately 1,000 small streams in Maryland during record drought and wet years in 2001-2003. We also investigated changes in nitrate-N export during the same time period in 8 intensively monitored small watersheds across an urbanization gradient in Baltimore, Maryland. Nitrate-N concentrations in Maryland were greatest in agricultural streams, urban streams, and forest streams respectively. During the period of record drought and wet years, nitrate-N exports in Baltimore showed substantial variation in 6 suburban/urban streams (2.9-15.3 kg/ha/y), 1 agricultural stream (3.4-38.9 kg/ha/y), and 1 forest stream (0.03-0.2 kg/ha/y). Interannual variability was similar for small Baltimore streams and nearby well-monitored tributaries and coincided with record hypoxia in Chesapeake Bay. Discharge-weighted mean annual nitrate concentrations showed a variable tendency to decrease/increase with changes in annual runoff, although total N export generally increased with annual runoff. N retention in small Baltimore watersheds during the 2002 drought was 85%, 99%, and 94% for suburban, forest, and agricultural watersheds, respectively, and declined to 35%, 91%, and 41% during the wet year of 2003. Our results suggest that urban land use change can increase the vulnerability of ecosystem nitrogen retention functions to climatic variability. Further work is necessary to characterize patterns of nitrate-N export and retention in small urbanizing watersheds under varying climatic conditions to improve future forecasting and watershed scale restoration efforts aimed at improving nitrate-N retention.

Identification of culturable stream water bacteria from urban, agricultural, and forested watersheds using 16S rRNA gene sequencing.

Bacteria present in water samples taken on a weekly basis, from June 2004 through June 2005, from three streams, were cultured on Coliscan Easygel agar plates. Colonies representative of a variety of colors and morphologies were subjected to amplification and sequencing of a 1000-1100 nt portion of the 16S rRNA gene. A total of 528 colonies were sequenced; these categorized into 26 genera and 78 species. Of 175 dark blue/purple colonies presumed to be E. coli, sequence analysis indicated that 45 (25%) were actually other genera. For the urban stream Gwynns Falls Gwynns Run, E. coli was the most common genus/species encountered, followed by Klebsiella and Aeromonas. For Pond Branch, a stream located in a forested watershed, it was Serratia, followed by Yersinia and Aeromonas. For McDonogh (MCDN), a stream associated with Zea mays (corn) row crop agriculture, E. coli was the most frequently isolated genus/species, followed by Aeromonas and Enterobacter. ERIC-PCR genotyping of isolates from the most prevalent genera/species, indicated a high degree of diversity within-stream for E. coli and K. pneumoniae. Conversely, genotyping of Y. enterocolitica isolates indicated that some were shared between different streams.

Impact of microbial diversity on rapid detection of enterohemorrhagic Escherichia coli in surface waters.

Enterohemorrhagic Escherichia coli (EHEC) are a physiologically, immunologically and genetically diverse collection of strains that pose a serious water-borne threat to human health. Consequently, immunological and PCR assays have been developed for the rapid, sensitive detection of presumptive EHEC. However, the ability of these assays to consistently detect presumptive EHEC while excluding closely related non-EHEC strains has not been documented. We conducted a 30-month monitoring study of a major metropolitan watershed. Surface water samples were analyzed using an immunological assay for E. coli O157 (the predominant strain worldwide) and a multiplex PCR assay for the virulence genes stx(1), stx(2) and eae. The mean frequency of water samples positive for the presence of E. coli O157, stx(1) or stx(2) genes, or the eae gene was 50%, 26% and 96%, respectively. Quantitative analysis of selected enriched water samples indicated that even in samples positive for E. coli O157 cells, stx(1)/stx(2) genes, and the eae gene, the concentrations were rarely comparable. Seventeen E. coli O157 strains were isolated, however, none were EHEC. These data indicate the presence of multiple strains similar to EHEC but less pathogenic. These findings have important ramifications for the rapid detection of presumptive EHEC; namely, that current immunological or PCR assays cannot reliably identify water-borne EHEC strains.

Increased salinization of fresh water in the northeastern United States.

Chloride concentrations are increasing at a rate that threatens the availability of fresh water in the northeastern United States. Increases in roadways and deicer use are now salinizing fresh waters, degrading habitat for aquatic organisms, and impacting large supplies of drinking water for humans throughout the region. We observed chloride concentrations of up to 25% of the concentration of seawater in streams of Maryland, New York, and New Hampshire during winters, and chloride concentrations remaining up to 100 times greater than unimpacted forest streams during summers. Mean annual chloride concentration increased as a function of impervious surface and exceeded tolerance for freshwater life in suburban and urban watersheds. Our analysis shows that if salinity were to continue to increase at its present rate due to changes in impervious surface coverage and current management practices, many surface waters in the northeastern United States would not be potable for human consumption and would become toxic to freshwater life within the next century.

tir- and stx-positive Escherichia coli in stream waters in a metropolitan area.

Diarrheagenic Escherichia coli, which may include the enteropathogenic E. coli and the enterohemorrhagic E. coli, are a significant cause of diarrheal disease among infants and children in both developing and developed areas. Disease outbreaks related to freshwater exposure have been documented, but the presence of these organisms in the urban aquatic environment is not well characterized. From April 2002 through April 2004 we conducted weekly surveys of streams in the metropolitan Baltimore, Md., area for the prevalence of potentially pathogenic E. coli by using PCR assays targeting the tir and stx(1) and stx(2) genes. Coliforms testing positive for the presence of the tir gene were cultured from 653 of 1,218 samples (53%), with a greater prevalence associated with urban, polluted streams than in suburban and forested watershed streams. Polluted urban streams were also more likely to test positive for the presence of one of the stx genes. Sequence analysis of the tir amplicon, as well as the entire tir gene from three isolates, indicated that the pathogenic E. coli present in the stream waters has a high degree of sequence homology with the E. coli O157:H7 serotype. Our data indicate that pathogenic E. coli are continually deposited into a variety of stream habitats and suggest that this organism may be a permanent member of the gastrointestinal microflora of humans and animals in the metropolitan Baltimore area.

Evaluation of parameters affecting quantitative detection of Escherichia coli O157 in enriched water samples using immunomagnetic electrochemiluminescence.

We report here the use of immunomagnetic (IM) electrochemiluminescence (ECL) for quantitative detection of Esherichia coli O157:H7 in water samples following enrichment in minimal lactose broth (MLB). IM beads prepared in-house with four commercial anti-O157 monoclonal antibodies were compared for efficiency of cell capture. IM-ECL responses for E. coli O157:H7 (strain SEA13B88) were similar for all four commercial anti-O157 LPS monoclonal antibodies. The ECL signal was linearly correlated with E. coli O157:H7 cell concentration, indicating a constant ECL response per cell. Twenty-two strains of E. coli O157:H7 or O157:NM gave comparable ECL signals using IM beads prepared in-house. To assess the potential for interference from background bacteria in MLB-enriched water samples, 10(4) cells of E. coli O157:H7 (strain SEA13B88) were added to enriched samples prior to analysis. There was considerable variability in recovery of E. coli O157:H7 cells; net ECL signals ranged from 1% to 100% of expected values (i.e., percent inhibition from 0% to 99%). Cultures of Klebsiella pneumoniae, Klebsiella oxytoca, and Enterobacter cloacae, subsequently isolated from MLB-enriched water samples via IM separation (IMS), were observed to interfere with the binding of E. coli O157:H7 cells to IM beads. Recoveries of 10(4) E. coli O157:H7 cells were