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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 r

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 resi

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. H

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.

Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 113 (2008): G02021, doi:10.1029/2007JG000482., Microbial activity in saturated, subsurface sediments in riparian forests may be supported by recent photosynthate or ancient (>500 ybp) soil organic carbon (SOC) in buried horizons. Metabolism of ancient SOC may be particularly important in riparian zones, considered denitrification hot spots, because denitrification in the riparian subsurface is often C-limited, because buried horizons intersect deep flow paths, and because low C mineralization rates can support ecosystem-relevant rates of denitrification. Buried horizons are common where alluvial processes (stream migration, overbank flow) have dominated riparian evolution. Our objectives were to determine: (1) the extent to which ancient SOC directly supports subsurface microbial activity; (2) whether different C sources support microbial activity in alluvial versus glaciofluvial riparian zones; and (3) how microbial use of ancient SOC varies with depth. In situ groundwater incubations and 14C dating of dissolved inorganic carbon revealed that ancient SOC mineralization was common, and that it constituted 31–100% of C mineralization 2.6 m deep at one site, at rates sufficient to influence landscape N budgets. Our data failed to reveal consistent spatial patterns of microbially available ancient C. Although mineralized C age increased with depth at one alluvial site, we observed ancient C metabolism 150 cm deep at a glaciofluvial site, suggesting that subsurface microbial activity in riparian zones does not vary systematically between alluvial and glaciofluvial hydrogeologic settings. These findings underscore the relevance of ancient C to contemporary ecosystem processes and the challenge of using mappable surface features to identify subsurface ecosystem characteristics or riparian zone N-sink strength., We are grateful to the Cornell Program in Biogeochemistry for graduate research grants and to the U.S. EPA for a STAR Graduate Fellowship to Noel Gurwick. Support for radiocarbon analyses also came from USDANRICGP grant 99–35102– 8266, NSF cooperative agreement OCE-9807266, and an Andrew W. Mellon Foundation grant to the Institute of Ecosystem Studies. A graduate research grant to N. Gurwick from the Theresa Heinz Scholars for Environmental Research provided salary for Pete Seitz-Rundlett.

Microbial activity in saturated, subsurface sediments in riparian forests may be supported by recent photosynthate or ancient (>500 ybp) soil organic carbon (SOC) in buried horizons. Metabolism of ancient SOC may be particularly important in riparian zones, considered denitrification hot spots, because denitrification in the riparian subsurface is often C-limited, because buried horizons intersect deep flow paths, and because low C mineralization rates can support ecosystem-relevant rates of denitrification. Buried horizons are common where alluvial processes (stream migration, overbank flow) have dominated riparian evolution. Our objectives were to determine: (1) the extent to which ancient SOC directly supports subsurface microbial activity; (2) whether different C sources support microbial activity in alluvial versus glaciofluvial riparian zones; and (3) how microbial use of ancient SOC varies with depth. In situ groundwater incubations and 14C dating of dissolved inorganic carbon revealed that ancient SOC mineralization was common, and that it constituted 31–100% of C mineralization 2.6 m deep at one site, at rates sufficient to influence landscape N budgets. Our data failed to reveal consistent spatial patterns of microbially available ancient C. Although mineralized C age increased with depth at one alluvial site, we observed ancient C metabolism 150 cm deep at a glaciofluvial site, suggesting that subsurface microbial activity in riparian zones does not vary systematically between alluvial and glaciofluvial hydrogeologic settings. These findings underscore the relevance of ancient C to contemporary ecosystem processes and the challenge of using mappable surface features to identify subsurface ecosystem characteristics or riparian zone N-sink strength.