Environmental Pollution 173 (2013) 138e149 Contents lists available at SciVerse ScienceDirect Environmental Pollution journal homepage: www.elsevier.com/locate/envpol Review Evaluating nutrient impacts in urban watersheds: Challenges and research opportunities Richard O. Carey a, *,1, George J. Hochmuth a, Christopher J. Martinez b, Treavor H. Boyer c, Michael D. Dukes b, Gurpal S. Toor d, John L. Cisar e a Soil and Water Science Department, University of Florida, PO Box 110510, Gainesville, FL 32611-0510, USA Department of Agricultural and Biological Engineering, University of Florida, PO Box 110570, Gainesville, FL 32611-0570, USA Department of Environmental Engineering Sciences, University of Florida, PO Box 116450, Gainesville, FL 32611-6450, USA d Soil and Water Science Department, Gulf Coast Research & Education Center, University of Florida, 14625 C.R. 672, Wimauma, FL 33598, USA e Environmental Horticulture Department, Ft. Lauderdale Research and Education Center, University of Florida, Ft. Lauderdale, FL 33314, USA b c a r t i c l e i n f o a b s t r a c t Article history: Received 18 July 2012 Received in revised form 11 October 2012 Accepted 17 October 2012 This literature review focuses on the prevalence of nitrogen and phosphorus in urban environments and the complex relationships between land use and water quality. Extensive research in urban watersheds has broadened our knowledge about point and non-point pollutant sources, but the fate of nutrients is not completely understood. For example, it is not known how long-term nutrient cycling processes in turfgrass landscapes influence nitrogen retention rates or the relative atmospheric contribution to urban nitrogen exports. The effect of prolonged reclaimed water irrigation is also unknown. Stable isotopes have been used to trace pollutants, but distinguishing sources (e.g., fertilizers, wastewater, etc.) can be difficult. Identifying pollutant sources may aid our understanding of harmful algal blooms because the extent of the relationship between urban nutrient sources and algal blooms is unclear. Further research on the delivery and fate of nutrients within urban watersheds is needed to address manageable water quality impacts. Ó 2012 Elsevier Ltd. All rights reserved. Keywords: Point source Non-point source Reclaimed water Septic systems Wastewater treatment facilities Isotopic analyses Stormwater 1. Introduction Urban watersheds are unique environments with characteristic disturbance gradients that alter natural biogeochemical cycles (Paul and Meyer, 2001; Beck, 2005; Kaye et al., 2006). Human activities control major factors driving these cycles, including land use change and soil variability, atmospheric chemistry, and hydrologic modifications (Kaye et al., 2006). Nitrogen (N) and phosphorus (P) are derived from multiple sources and pathways in urbanized watersheds and thus the relative proportion and spatial configuration of urban land use affect nutrient inputs to surface and groundwater (Basnyat et al., 1999; Groffman et al., 2004; Brett et al., 2005; Carey et al., 2011b). Common pollutant sources include stormwater runoff, atmospheric deposition, and wastewater * Corresponding author. E-mail address: [email protected] (R.O. Carey). 1 Present address: Department of Natural Resources and Environment, Earth Systems Research Center, Institute for the Study of Earth, Oceans, and Space, University of New Hampshire, Durham, NH 03824, USA. 0269-7491/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.envpol.2012.10.004 treatment systems (Grimshaw and Dolske, 2002; Schueler, 2003; Andersen et al., 2004). In urban watersheds, impervious surfaces (e.g., roads, driveways, walkways, etc.), stormwater management projects, and artificial drainage systems (e.g., canals), disrupt natural hydrological pathways and may enhance nutrient transport (Arnold and Gibbons, 1996; Caccia and Boyer, 2007; Bell and Moss, 2008; NRC, 2008). Nitrogen and P are critical to the ecological health of aquatic ecosystems, but excessive nutrient loading leads to undesirable consequences such as cultural eutrophication (Smith et al., 1999; Pinckney et al., 2001; Conley et al., 2009). Characteristic problems associated with eutrophic systems include the development of toxic and non-toxic algal blooms (Glibert et al., 2006; Bricker et al., 2008; Heisler et al., 2008). Algal blooms can limit light to submerged aquatic vegetation, reduce water transparency, and produce hypoxic or anoxic conditions (i.e., “dead” zones) that have adverse effects on fish populations (Smith et al., 1999; Heisler et al., 2008). Developing strategies to reduce overall nutrient exports from urban watersheds require an assessment of relative contributions from nutrient sources and pollutant transport mechanisms (Basnyat et al., 1999; Carey et al., 2011a, 2011b). Key aspects of R.O. Carey et al. / Environmental Pollution 173 (2013) 138e149 urban water quality research include analyzing land use-water quality relationships and identifying specific nutrient sources (Beaulac and Reckhow, 1982; Wickham and Wade, 2002; Wickham et al., 2002). Stable isotope analysis has been used to trace pollutants, especially N and P inputs that can potentially impair the ability of water resources to meet designated uses (e.g., fishing, recreation, etc.) (Widory et al., 2005; McLaughlin et al., 2006; Kendall et al., 2007). However, the relationship between nutrient inputs and water quality impacts is complex; algal blooms may occur independent of human influences and elevated nutrients may not produce blooms (Steidinger et al., 1999; Lenes et al., 2001; Walsh and Steidinger, 2001; Heisler et al., 2008). The objective of this review is to synthesize current knowledge on major urban pollutant sources delivering nutrients to aquatic systems and the challenges of evaluating water quality relationships in urban environments. Carey et al. (2012a) reviewed turfgrass fertilizer management practices and the implications for urban water quality. Turfgrass fertilization is briefly discussed in this paper within the context of other nutrient sources. Specific aspects of urban water quality discussed include: (1) watershed nutrient sources; (2) isotopic analyses to distinguish nutrient sources; (3) the effect of landscape composition and configuration on nutrient exports; and (4) the relationship between watershed nutrient exports and water quality impacts, using the development of algal blooms as an example. Research gaps pertaining to these issues are also identified. 2. Urban watersheds: non-point sources 2.1. Stormwater runoff and leaching Precipitation events that occur on impervious surfaces, or that exceed the infiltration or saturation capacity of soils, produce stormwater runoff. Typical nutrient concentrations in urban stormwater runoff in the U.S. are 2.0 mg L1 for total N (TN) and 0.26 mg L1 for total P (TP) (Schueler, 2003). A variety of factors in urban watersheds contribute to nutrient concentrations in runoff. Limited data exist on nutrient inputs from pet waste, but this can be substantial (Baker et al., 2001; Groffman et al., 2004; Fissore et al., 2012). Estimated N inputs from pet waste (17 kg N ha1 yr1) in a suburban watershed in Baltimore, Maryland exceeded contributions from fertilizers (14.4 kg N ha1 yr1) and atmospheric deposition (11.2 kg N ha1 yr1) (Baker et al., 2001; Groffman et al., 2004). Pet waste in the Minneapolis-Saint Paul, Minnesota region represented 84% of P inputs due to phosphate (PO4) fertilizer restrictions (Fissore et al., 2012). Fertilizer restrictions are intended to improve water quality because fertilizer management practices can lead to nutrient exports from turfgrass and landscape plants during precipitation events and melting snow. Management practices that influence nutrient retention include the type (i.e., soluble or controlledrelease), rate, and timing of fertilization (Engelsjord and Singh, 1997; Easton and Petrovic, 2004; Shober et al., 2010; Carey et al., 2012a). Established (mature) turfgrass receiving appropriate fertilizer applications typically leach less than 5% of applied N (Barton and Colmer, 2006). However, recycling grass clippings without adjusting (downward) fertilizer rates increases the potential for nutrient losses (Kopp and Guillard, 2002). Qian et al. (2003) simulated the long-term effects of returning clippings to Kentucky bluegrass grown on a clay loam soil while continuously using a fertilization rate of 150 kg N ha1 yr1. Leaching rates under this scenario were minimal (<2 kg N ha1 yr1) 20e30 years after establishment, but gradually increased (50e60 kg N ha1 yr1 after 100 years) as carbon and N sequestration declined. In addition to fertilization, irrigation practices (e.g., rate, frequency, etc.), species 139 variability (e.g., cool and warm season grasses, nutrient uptake efficiencies, etc.), and soil characteristics (e.g., texture, structure, etc.) determine whether turfgrass retains or exports nutrients (Trenholm et al., 1998; Barton and Colmer, 2006; Bowman et al., 2002). For example, turfgrass with dense ground cover reduces sediment and P losses in runoff (Linde et al., 1995). Urban watersheds now increasingly include green roofs and fertilizer applications, plant species, rainfall rates, and substrate characteristics are among several factors that influence pollutant loads from these systems (Berndtsson, 2010; Rowe, 2011). Green roofs collect atmospheric pollutants, attenuate heat island effects, and reduce runoff volumes compared to non-vegetated roofs, but function as pollutant sources or sinks during precipitation events. Berndtsson et al. (2006) revealed differences in nutrient exports from an extensive green roof system (0.95 ha) after comparing annual TN and TP loads in precipitation (TN: 9.1 kg ha1 yr1; TP: 0.2 kg ha1 yr1) and runoff (TN: 3.8 kg ha1 yr1; TP: 1 kg ha1 yr1). Green roofs located in areas receiving intense storms are particularly susceptible to nutrient exports (NRC, 2008). Hathaway et al. (2008) demonstrated that the growth media used for green roofs contributes to nutrient losses. Green roofs containing 15% compost leached nutrients and contributed to greater TN and TP outflow concentrations compared to rainfall alone or non-vegetated roofs. The type of fertilizers used on green roofs during the initial establishment period also contributes to nutrient losses (Berndtsson et al., 2006). Landfills accumulate nutrients from various waste products (e.g., lawn and household waste, biosolids, etc.) and are another source of urban pollutants (Kjeldsen et al., 2002; Louis, 2004; Renou et al., 2008). Precipitation percolating through waste layers leads to various physical, chemical, and microbial processes that generate leachate through interactions between landfill constituents and groundwater (Christensen et al., 2001). Factors affecting the quantity and quality of landfill leachate flow include landfill age, design specifications such as liners, the degree of waste compaction, climate variability, and the inherent properties of waste products (Renou et al., 2008). Carey et al. (2012b) described regulatory and resource management practices associated with nutrient exports from municipal solid waste facilities such as landfills. Construction activities (e.g., new subdivisions, commercial centers, highways, etc.) contribute nutrients to urban stormwater runoff as elevated erosion rates during construction facilitate the transport of sediment-bound P (Carpenter et al., 1998; Atasoy et al., 2006). Line et al. (2002) reported sediment export during the clearing and grading phase of construction (referred to as a construction-I site) in North Carolina was 10 times greater than other land uses (single-family residential, golf course, dairy cow pasture, etc.). However, average nutrient exports from a construction-II site (TN: 36.3 kg ha1 yr1; TP: 1.3 kg ha1 yr1), which includes drainage infrastructure installation and the housebuilding phase, differed from the construction-I site (TN: 8.3 kg ha1 yr1; TP: 3.0 kg ha1 yr1). Total N exports from a residential area (23.9 kg ha1 yr1) and golf course (31.2 kg ha1 yr1) were similar to the construction-II site, but TN rates from a pasture (6.7 kg ha1 yr1) and wooded area (11.4 kg ha1 yr1) were similar to the construction-I site (Line et al., 2002). In another study, sediment export from a developing subdivision was 95% greater than forested/agricultural areas (Line and White, 2007). Both TN (15.5 kg ha1 yr1) and TP (1.3 kg ha1 yr1) loads from the subdivision exceeded rates from the undeveloped areas (TN: 6.3 kg ha1 yr1; TP: 0.5 kg ha1 yr1). Local conditions (e.g., climate, soil, and topographic characteristics) affect sediment export from construction sites. Burton and Pitt (2001) noted that intense rainfall, soil erodibility, and steep terrain produced high erosion rates in Birmingham, Alabama, 140 R.O. Carey et al. / Environmental Pollution 173 (2013) 138e149 which amplified the impact of even small construction projects. Stormwater pollutant exports associated with construction sites may continue for several years until soils become stabilized postdevelopment and then impervious surfaces dictate runoff characteristics (NRC, 2008). 2.2. Atmospheric deposition Atmospheric deposition can be a source of both N and P to surface waters, but N deposition is greater in magnitude than P; the vast majority (90%) of P deposition from air is due to wind-eroded particles (Smil, 2000). Monitoring programs in the U.S. (e.g., National Atmospheric Deposition Program) and Europe (e.g., European Monitoring and Evaluation Programme) measure N wet deposition (precipitation) rates, but dry deposition (gases and particles) of N continues to be difficult to measure (Holland et al., 2005). Only a fraction of dry deposition is usually measured, with some gases (e.g., NO, NO2, NH3, etc.) excluded from dry deposition monitoring programs (Pyke et al., 2008). Land use affects atmospheric deposition because agricultural activities such as livestock operations produce reduced N (e.g., NH3eN) emissions. Fossil fuel combustion produces N oxides (NO and NO2; called NOx), which are converted to nitric acid and nitrate aerosols. These atmospheric conversion processes enhance pollutant transport and increase the potential impact radius. Reduced N (NH3eN) is deposited much more rapidly than oxidized N, thereby limiting the impact of agricultural emissions to local areas (Spokes and Jickells, 2005). Catalytic converters in vehicles also release NH3eN as a byproduct of the process to convert NOx to N2; NH3eN is released in reducing conditions (e.g., high fuel to air ratio during acceleration), producing elevated NH3eN deposition rates along major roads (Kirchner et al., 2005; Bernhardt et al., 2008). Maestre and Pitt (2005) provided further evidence of the relationship between automobiles and localized NH3eN deposition as freeway runoff contained the highest NH3eN concentrations among various U.S. land uses. Emission rates vary for different types of vehicles but range from 10 to 155 mg NH3eN km1 of roads (Emmenegger et al., 2004). The potential contribution from runoff highlights the fact that both direct deposition onto water surfaces and deposition within watersheds affect receiving waters. For estuaries with a surface water to watershed area ratio greater than 0.2, direct deposition typically contributes at least 20% of the TN loads. If this ratio is below 0.1, less than 10% of TN loads derive from direct deposition (Valigura et al., 2000). Poor (2002) estimated 816,466 kg N were directly deposited onto the surface of Tampa Bay, Florida in 2001. From 1999 to 2003, atmospheric deposition contributed 21% of N loads to the estuary (Anderson, 2006). In contrast to Tampa Bay, Caccia and Boyer (2007) estimated only 12% of N loads to Biscayne Bay, Florida were derived from direct atmospheric inputs, with the remaining 88% of N inputs from canals. However, Caccia and Boyer (2007) did not evaluate the contribution of atmospheric deposits on landscape surfaces to canal loads. In a study conducted in Phoenix, Arizona, Hope et al. (2004) suggested parking lot surfaces could accumulate dry-deposited nutrients in arid urban watersheds between rainfall events and contribute to nutrient loading during runoff, although nitrateeN (NO3eN) and ammoniumeN (NH4eN) could be transformed prior to entering surface waters. For example, in the Chesapeake Bay watershed, only 22% of atmospheric N deposition is transported to the estuary (Castro et al., 2003). 2.3. Septic systems Onsite sewage treatment and disposal systems, which include septic systems, have been used in the U.S. since the late 19th century. The U.S. Census Bureau officially began counting the number of homes using these systems in 1960, when 14 million homes were identified (Rome, 2001). Later reports included estimates from 1985 (24.6 million) and 2007 (26.1 million), with the 2007 estimate representing 20% of all U.S. homes (USEPA, 2008). Rural and suburban areas often lack centralized wastewater treatment, thereby influencing the distribution of onsite treatment systems. In 2007, 97% of U.S. housing units with septic systems were located in either rural (50%) or suburban settings (47%) (USEPA, 2008). Septic system densities can be particularly high in areas experiencing a surge in new development (Marella, 2004). Groundwater contamination caused by N loading from septic systems is a primary concern (Gold et al., 1990; Wernick et al., 1998). Subsurface septic systems treat wastewater by using septic tanks to separate liquid and solid components before discharging effluent to surrounding absorption systems or drainfields containing distribution pipes. Septic tanks discharge approximately 280 L per capita d1 and effluent concentrations (40e80 mg TN L1) typically contain a mixture of 75% NH4eN and 25% organic-N (Novotny and Chesters, 1981; Novotny et al., 1989). As effluent percolates through the soil beneath the drainfield, NH4eN and organic-N are oxidized in the unsaturated zone to NO3eN. The N removal efficiency of septic systems determines the potential for NO3eN loading to groundwater. Conventional systems remove 10e 44% of TN from wastewater, but alternative systems with anaerobic up-flow filters (40e75%) and recirculating sand filters (60e85%) remove more TN by enhancing nitrificationedenitrification processes (USEPA, 1993; NRC, 2000). Soil characteristics (e.g., temperature, density, conductivity, etc.) are additional factors influencing N loading rates to groundwater (NRC, 2000; Bernhardt et al., 2008). Septic system failure rates can range from 5 to 40% and include hydraulic, subsurface, and treatment malfunctions (Swann, 2001). Hydraulic failures reflect clogged systems, subsurface failures produce partially treated wastewater plumes, and treatment failures occur when pollutants are not sufficiently removed from wastewater. Pollutants from septic systems enter receiving waters as a result of hydraulic failures that cause effluent to emerge onto the surface of drainfields or through subsurface transport to groundwater. High water tables may also interfere with the effectiveness of septic systems to treat wastewater because submerged drainage networks become directly linked to surrounding water systems (Bocca et al., 2007). Coastal communities with naturally high water tables consequently have an increased risk of water quality impairment from septic systems. If conditions facilitate NO3eN transport, N delivery rates from septic systems can be similar to inputs from row crop production. Gold et al. (1990) measured NO3eN in shallow groundwater from various land uses and reported values for fertilized cornfields (66 kg ha1 yr1), septic systems (48 kg ha1 yr1), fertilized lawns (6 kg ha1 yr1), and unfertilized lawns (1.4 kg ha1 yr1). Morgan et al. (2007) reported NO3eN loadings from on-site wastewater systems in La Pine, Oregon increased from 1700 kg N yr1 in 1960 to 41,000 kg N yr1 in 2005, due to septic tanks associated with residential development. Additional residential lots are available for development in this area and NO3eN loading to groundwater could increase to 68,000 kg N yr1 by 2019 (Morgan et al., 2007). Groundwater N derived from septic systems eventually contributes to surface water nutrient inputs. Wernick et al. (1998) evaluated water quality in Vancouver, Canada where increased NO3eN concentrations in streams corresponded with watershed septic system densities. For estuaries and watersheds, septic systems can be a major component of overall N budgets (Fig. 1). Buttermilk Bay, Massachusetts (74%), Buzzards Bay, Massachusetts (16%), Charleston Harbor, South Carolina (15%), and Narragansett R.O. Carey et al. / Environmental Pollution 173 (2013) 138e149 Bay, Rhode Island (11%) all receive TN inputs derived from septic systems (Horsley and Witten, 1994; Castro et al., 2003). In coastal communities of Taylor County, Florida, where there is a heavy reliance on septic systems, the occurrence of both elevated bacterial and TN concentrations in coastal waters suggests that septic systems can also contribute more nutrients than runoff in certain local areas (Bocca et al., 2007). Compared to N, P delivery to ground and surface waters is less of a concern because of the ability of most soils to retain P. Soil mineralogy determines P removal efficiency as clay minerals and metal oxides (iron and aluminum) enhance PO4 sorption, while calcareous soils remove PO4 through precipitation reactions (Jones and Lee, 1979). Additional factors affecting the potential for P contamination include soil pH and the distance between septic systems and the water table. Soils can retain up to 95% of P, with adsorption and precipitation reactions occurring within a few meters of the drainfield (Mandel and Haith, 1992). For example, soils rich in calcium carbonate can limit P migration (Lapointe et al., 1990; Meeroff et al., 2008). Conditions that may reduce nutrient retention and enhance pollutant transport include septic systems that are located immediately adjacent to water bodies, soils with reduced adsorption capacities (e.g., sandy or P-saturated soils), and elevated water tables (Jones and Lee, 1979; Swann, 2001; Briggs et al., 2008; Meeroff et al., 2008). Products that increase household P outputs, such as laundry and dishwasher detergents containing PO4, provide more opportunities for P transport. Early detergent formulations included P builders 141 (e.g., sodium tripolyphosphate) that removed water hardness and enhanced cleaning, but increased P delivery to aquatic systems (Jenkins et al., 1973; Kehoe, 1992; Litke, 1999). In 1967, at the peak of P detergent use in the U.S., manufacturing processes consumed approximately 220,000 metric tons of P (Litke, 1999). Several states have since instituted PO4 detergent bans and the industry voluntarily stopped manufacturing domestic laundry detergents with PO4 in the 1990s. Both actions have reduced the contribution of laundry detergents to urban watershed nutrient budgets (Hoffman and Bishop, 1994; Litke, 1999). Statewide bans typically target laundry detergents, but dishwasher detergents and household cleaning products still contain PO4 (Litke, 1999). The acknowledgment that PO4 in dishwasher detergents can also reduce water quality has led to specific PO4 bans for these products in sixteen states (NYS, 2010). 3. Urban watersheds: point sources 3.1. Wastewater treatment plants Centralized wastewater treatment plants (WWTPs) process wastewater from multiple sources before discharging effluent to surface and/or groundwater. Although WWTPs require discharge permits and monitoring programs ensure compliance with regulatory standards, the nutrient content of discharged effluent can vary considerably depending on the level of wastewater treatment. Primary treatment targets large objects and suspended solids; secondary treatment removes additional organic material that Fig. 1. Relative nitrogen inputs by source to (a) several estuaries draining urban watersheds (Castro et al., 2003) and (b) receiving waters of the Wekiva Study Area, Central Florida (Roeder, 2008). The wastewater category in (a) includes effluent from wastewater treatment plants (WWTPs) and septic systems. 142 R.O. Carey et al. / Environmental Pollution 173 (2013) 138e149 remains in the effluent after primary treatment; and tertiary or advanced treatment reduces nutrient and metal concentrations (Tchobanoglous et al., 2003). Concentration ranges for TN in untreated wastewater (20e70 mg L1), wastewater receiving secondary treatment (15e35 mg L1), and wastewater receiving advanced treatment (1e8 mg L1) reflect the variability of N concentrations in discharged effluent (Asano et al., 2007; Tchobanoglous et al., 2003). Total P concentrations in wastewater receiving secondary treatment (4e10 mg L1) are also greater than discharged effluent receiving advanced treatment (0.5e2 mg L1) (Tchobanoglous et al., 2003; Asano et al., 2007). Effluent from WWTPs can provide consistent nutrient loads to receiving waters that exceed contributions from non-point sources (Carey and Migliaccio, 2009). The discharge volume from WWTPs is an important factor affecting overall nutrient loads. These facilities can dominate (>70% by volume) downstream flows (Andersen et al., 2004; Ekka et al., 2006) and deliver large loads even if effluent contains low nutrient concentrations. During naturally low-flow periods, effluent concentrations and discharge volumes become an even greater concern for downstream areas (Andersen et al., 2004). Important land use and water quality relationships in urban watersheds may therefore be obscured by the overwhelming influence of WWTP discharges (Miltner et al., 2004). For example, Andersen et al. (2004) compared stream water quality at multiple sites in South Carolina and average NO3eN and soluble reactive phosphorus (SRP) concentrations downstream from two WWTPs (NO3eN: 50.5 mg L1 and SRP: 3.7 mg L1) were considerably higher than upstream measurements (NO3eN: 1.6 mg L1 and SRP: 0.3 mg L1). The use of reclaimed (reuse) water from WWTPs may additionally contribute to nutrient exports from urban watersheds because reuse applications (e.g., landscape irrigation, groundwater recharge, and non-potable urban uses) apply varying levels of wastewater and associated nutrients (Swancar, 1996; Asano et al., 2007; Carey and Migliaccio, 2009). Conventional fertilizers are often used with reclaimed water to balance nutrient ratios or to supplement overall nutrient requirements for landscape plants (Sala and Mujeriego, 2001; Martinez and Clark, 2009). Swancar (1996) compared six pairs of golf courses irrigated with either reclaimed water or groundwater and concluded that the type of irrigation affects shallow groundwater quality due to higher percentages of constituents such as NO3eN in reclaimed water. Seasonal differences in nutrient uptake efficiencies may additionally lead to leaching or runoff. Effluent is commonly applied to bermudagrass in the southern U.S. to utilize its ability to assimilate nutrients, but Wherley et al. (2009) cautioned against year-round dispersal due to differences in NO3eN uptake during the active growth period in summer (>90%), fall and spring transition months (80e90%), and winter dormancy (10e20%). Landscape irrigation (e.g., golf courses, parks, residential areas, etc.) is second to agricultural irrigation in terms of reclaimed water use in the U.S. Utilizing reclaimed water has been an ongoing priority in states such as Florida, where the total reuse capacity of domestic WWTPs has increased from 1.4 Mm3 d1 in 1986 to 5.2 Mm3 d1 in 2006 (SFWMD, 2008). Dual distribution systems that deliver both potable and reclaimed water have operated in St. Petersburg, Florida since 1977 and residents were originally encouraged to use un-metered reclaimed water for irrigation (Okun, 2000; USEPA, 2004). The majority of operators distributing reclaimed water now charge a fee to conserve this resource (FDEP, 2010), and this fee influences the volume of reclaimed water used per customer (USEPA, 2004). Knowledge of the nutrient content of reclaimed water, nutritional requirements of landscape plants, and the effect of long-term applications may improve nutrient retention and assimilation when using reclaimed water for irrigation. 4. Distinguishing nutrient sources Development of effective nutrient control measures requires an assessment of contributing sources. Stable isotopes can help to differentiate nutrient sources and explore pollutant pathways that lead to water quality impairment (Heaton, 1986; Peterson and Fry, 1987; Mayer et al., 2002). Chemical properties for stable isotopes used in ecological research include low atomic masses and large relative mass differences for rare and abundant species (Sulzman, 2007). Both N (14N and 15N) and oxygen (16O, 17O, and 18O) stable isotopes provide clues about nutrient sources. The 14N isotope represents 99.64% of atmospheric N and 15N represents 0.36%. Oxygen isotopes share a similar distribution (16O: 99.76%; 17O: 0.04%; and 18O: 0.20%). Isotopic ratios (15N/14N, 17O/16O, or 18O/16O) for measured samples are reported in terms of d15N, d17O, and d18O values, which are parts per thousand differences (&) from ratios in accepted standards (N: atmosphere; oxygen: Vienna Standard Mean Ocean Water). The following equation is used to determine isotopic compositions (&) of samples: d 15 Nsample or d 18 Osample ¼ Rsample Rstandard . Rstandard 1000 where R is the isotopic ratio for samples and standards. Pollutant sources in the environment have characteristic isotopic composition ranges. Typical d15N values for synthetic fertilizers (0 4&) are lower than values for human or animal wastewater (>þ10&) (Table 1) (Gormly and Spalding, 1979; Heaton, 1986; Lapointe and Bedford, 2007). Synthetic fertilizers and wastewater can combine to produce mixed-range d15N values (þ4.3 to þ8.7&), as measured in samples from several Florida springs (Toth, 2003). Differences in d15N values among pollutant sources arise because fractionation mechanisms change isotopic ratios (Sulzman, 2007). Commercial fertilizer production occurs with limited isotopic fractionation because of the industrial fixation of atmospheric N, creating fertilizers with d15N values approaching zero. In contrast, fractionation associated with the conversion of urea to ammonia, as well as ammonia volatilization and coupled nitrification and denitrification processes, contribute to elevated d15N values from septic systems and WWTPs (Heaton, 1986). However, wastes from human and animal sources have similar d15N values (Table 1) (Curt et al., 2004). Organic fertilizers (e.g., from animal sources) can have d15N values (þ2 to þ30&) that are indistinguishable from wastewater (Kendall et al., 2007). Characteristic d15N values for N derived from natural soil organic N (3 to þ5&) and atmospheric deposition (10 to þ8&) also overlap with values for synthetic fertilizers (Mayer et al., 2002). Relying solely on N isotopes to identify pollutant sources is consequently problematic. Table 1 Sample nitrogen isotopic compositions (d15N) from different sources. Nitrogen sourcea Synthetic fertilizers Ammonium nitrate Ammonium sulfate Urea Animal waste Swine manure Poultry manure Dairy cattle manure WWTPs Sludge Effluent a Curt et al. (2004). Mean d15N (&) 1.46 2.32 1.16 1.46 1.28 0.33 13.82 7.03 10.98 4.44 12.19 2.69 11.42 7.21 11.61 2.71 R.O. Carey et al. / Environmental Pollution 173 (2013) 138e149 Several researchers have used multiple isotopes to investigate N transport, cycling, and resultant effects on water quality. Widory et al. (2005) combined N and boron isotopes to trace pollutants and identified WWTP effluent as the main source of NO3eN in subsurface alluvial groundwater. Boron helped to identify this source because of differences between d11B values for cattle manure (þ11.6& to þ19.2&) and wastewater effluent (1.8 0.1&) (Widory et al., 2005). A widely used technique for tracing the origin of NO3eN involves calculating both d15N and d18O values, due to typical isotopic ranges for NO3eN derived from fertilizers, atmospheric deposition, and wastewater (Fig. 2). Both 15 N and 18O isotopes are also useful to determine the significance of N cycling processes (e.g., denitrification or nitrification) on NO3eN (Aravena et al., 1993; Mayer et al., 2002; Kendall et al., 2007). Nitrogen cycling can mask nutrient sources by changing isotopic ratios during processes such as denitrification. Kendall et al. (2007) discussed several methods to account for both N cycling and mixing among several pollutant sources, including the use of multiple isotopes. For example, Aravena et al. (1993) differentiated NO3eN in septic system plumes from fertilizer-derived concentrations in groundwater using d15N and d18O. Aravena et al. (1993) also identified nitrification of NH4eN, from wastewater and fertilizers, as the source of NO3eN. Phosphorus is monoisotopic, unlike N, but inorganic and organic PO4 can be traced indirectly using d18O of PO4 (d18OP). Gruau et al. (2005) doubted the use of d18OP values to identify pollutant sources because of the restricted isotopic difference between fertilizers (þ19.6& to þ23.1&) and WWTP effluent (þ17.7& to þ18.1&). Biogeochemical cycling of P, including processes such as adsorption that may result in isotopic fractionation, and the rapid equilibration between d18OP and d18O in ambient water, can result in d18OP values that reflect equilibrium values, not the isotopic characteristics of pollutant sources (Blake et al., 2005; Young et al., 2009). Systems that are not P-limited and exhibit large differences between d18OP and d18O in water, such as estuaries, create suitable conditions to trace PO4 (McLaughlin et al., 2006; Kendall et al., 2007). Young et al. (2009) compiled mean d18OP values for various sources, including fertilizers (þ20.2&), aerosols (þ20.5&), detergents (þ16.9&), vegetation (þ16.9&), and WWTPs (þ13.4&). Statistical comparisons (Student’s t-Test) of data from multiple studies indicated fertilizers had significantly (p < 0.05) higher d18OP values than all other sources except aerosols; d18OP values for WWTP effluent were significantly lower than other sources (Young et al., 2009). 80 70 60 Atmospheric Deposition (‰) 40 18O 50 30 Trend During Denitrification Fertilizers 20 10 Nitrification in Soils 0 Sewage and Manure -10 -20 -10 0 10 15N 20 30 40 (‰) Fig. 2. Isotopic compositions (d15N and d18O) for nitrateenitrogen derived from different sources (Mayer et al., 2002). 143 Combining stable isotope analysis with additional data and techniques provides further options to distinguish sources. Bleifuss et al. (2000) analyzed d15N values as well as dissolved oxygen and sodium concentrations from public wells in New York and determined that residential, as opposed to agricultural, NO3eN sources were primarily responsible for contaminated water. Isotopic compositions in aquatic organisms have also been used as proxies to trace N sources (Steffy and Kilham, 2004; Ulseth and Hershey, 2005; Vander Zanden et al., 2005). Nash and Halliwell (2000) discussed several biological markers (e.g., sterols and phospholipids) that could complement stable isotope techniques identifying PO4 and sediment sources. Stable isotope analysis can be a useful tool to identify nutrient sources contributing to water quality impairment (Heaton, 1986; Peterson and Fry, 1987; Zohar et al., 2010). However, potential pollutant sources often have overlapping isotopic ranges that can complicate nutrient analysis (Mayer et al., 2002; Gruau et al., 2005; Kendall et al., 2007). Fractionation mechanisms that occur during nutrient cycling create additional complications by changing typical isotopic characteristics of pollutants (Blake et al., 2005; Young et al., 2009), though this could be used to identify mitigating processes (e.g., denitrification). Utilizing multiple isotopes and tracers increases the likelihood of accurately identifying pollutant sources (Aravena et al., 1993; Widory et al., 2005; Kendall et al., 2007; Kaushal et al., 2011). Questions still remain about spatial and temporal influences on isotopic compositions from different sources and techniques to distinguish multiple sources from the same general category (e.g., atmospheric deposition). The emergence of in situ sensors for carbon and nutrients provides new opportunities to distinguish sources by integrating multiple instruments operating at fine temporal resolutions that could be coupled with isotope sampling. Strategic use of in situ sensors can potentially reveal simultaneous biogeochemical processes (nutrient uptake, transformation, etc.) occurring during hydrologically variable conditions (Pellerin et al., 2011; Heffernan and Cohen, 2010). Pairing sensors with techniques such as stable isotope enrichment could expand currently limited data on the source and fate of nutrients during storm events in developing watersheds. 5. Landscape composition and configuration Nutrient exports reflect the relative proportion and spatial distribution of watershed land use/land cover (LULC) (Basnyat et al., 1999; Groffman et al., 2004; Carey et al., 2011b). Anthropogenic influences in urban and agricultural watersheds produce overall water quality characteristics that contrast with predominantly forested watersheds. During baseline conditions over a ten-year period (1990e1999) in Seattle, Washington, average TN, TP, and dissolved P concentrations for urban streams were 44%, 95%, and 122% greater, respectively, than forested streams (Brett et al., 2005). Similar elevated nutrient discharges from agricultural watersheds derive from variability associated with soils, crops, fertilizer applications, fertilizer storage facilities, and management practices such as soil tillage methods (Beaulac and Reckhow,1982; Sims et al.,1998; Nair et al., 2004). The greater distribution of watershed forest cover relative to urban and/or agricultural land use consequently corresponds to decreased N and P exports (Beaulac and Reckhow, 1982; Basnyat et al., 1999; Groffman et al., 2004). Wickham and Wade (2002) used LULC nutrient export coefficients to assess the risk of nutrient exports from small watersheds in Maryland. For watersheds with less than 70% forest cover, the relative proportion of urban land use dramatically increased risk estimates for P (Wickham and Wade, 2002). Wickham et al. (2002) modeled alternative land use change scenarios in the mid-Atlantic region of the U.S. to identify 144 R.O. Carey et al. / Environmental Pollution 173 (2013) 138e149 areas most vulnerable to increased N and P exports. Areas with a forested to agricultural ratio of 6:1, and projected urbanization rates 20%, were vulnerable to increased N exports; at similar urbanization rates, P vulnerability increased in areas with a 2:1 forested to agricultural ratio (Wickham et al., 2002). Impervious surfaces in urban watersheds increase runoff volumes and enhance nutrient transport compared to pervious ground cover characterized by lower runoff coefficients. Unpaved parking areas and other locations with compacted soils that hinder infiltration are considered functionally impervious surfaces (NRC, 2008). The effect of watershed imperviousness on nutrient export is particularly evident at higher, less frequent discharges (Shields et al., 2008). Bannerman et al. (1993) identified streets as a major source of pollutants in Wisconsin stormwater. Elevated runoff volumes from impervious surfaces, compared to other land uses, increased pollutant loads. Automobile-related sources (e.g., fluids from parking lots, service stations, automobile exhaust, etc.) contribute nutrients to stormwater systems and thus street traffic volume is another factor affecting nutrient loads. Steuer et al. (1997) investigated contamination sources in an urban watershed draining to Lake Superior in Michigan and although nutrient runoff concentrations from lawns (TN: 9.70 mg L1; TP: 2.33 mg L1) were five to ten times higher than other areas, concentrations from hightraffic streets (TN: 2.95 mg L1; TP: 0.31 mg L1) were greater than low-traffic streets (TN: 1.17 mg L1; TP: 0.14 mg L1). The type of driveway in residential areas also influences nutrient export because impervious driveways can generate greater runoff volumes and nutrients loads compared to permeable paver driveways (Gilbert and Clausen, 2006). A conservative estimate of impervious cover for the conterminous U.S. in 2000 was 8 million ha and is projected to exceed 11 million ha by 2030 (Theobald et al., 2009). Total impervious area (TIA) in developing watersheds is used as an indicator of aquatic health because a threshold of 5e10% TIA can impair water quality due to urbanization effects (Schiff and Benoit, 2007). Exum et al. (2005) suggested 5e10% TIA produces modest impacts related to urbanization that can be addressed through planning and watershed management. Urbanization leads to significant aquatic degradation at 10e20% TIA, but the likelihood of successful remediation efforts to improve water quality under this scenario is greater than watersheds exceeding 20% TIA (Exum et al., 2005). In addition to total watershed imperviousness, another metric to evaluate pollutant pathways is effective imperviousness, the directly connected impervious area (DCIA) that is hydrologically linked to drainage conveyance systems. The difference between TIA and DCIA is that TIA includes surfaces such as roofs that can drain to pervious areas (e.g., lawns), but runoff from DCIA will directly enter drainage systems and/or receiving waters. In Wisconsin, Bannerman et al. (1993) noted that streets were 100% connected to the stormwater system while roofs were only 2% connected. Watershed DCIA percentage consequently has a greater potential than the equivalent TIA percentage to influence nutrient loads exported in stormwater runoff (Brabec et al., 2002). Lee and Heaney (2002) investigated the importance of DCIA percentage in a residential area of Miami, Florida by analyzing runoff-rainfall relationships during a 52-year period. Although DCIA constituted 44% of the watershed in this study, DCIA generated 72% of the runoff (Lee and Heaney, 2002). The DCIA percentage in urban watersheds is a critical factor determining the extent of first-flush runoff effects and nutrient removal mechanisms required to improve stormwater quality (Harper and Baker, 2007). Several researchers have investigated the relationship between the spatial characteristics of LULC and water quality (Lowrance et al., 1984; Basnyat et al., 1999; Lee et al., 2009). Carey et al. (2011b) identified spatially explicit LULC variables, including the proximity of specific types of urban development to aquatic systems, which corresponded to increased nutrient exports. Forested watersheds are particularly effective at reducing nutrient exports because these areas function as active nutrient transformation zones or sinks (Lowrance et al., 1984; Basnyat et al., 1999). Properly managed riparian zones in agricultural and urban watersheds also reduce nutrient transport (Norris, 1993; Groffman et al., 2002; Correll, 2005). However, hydrological modifications in urban watersheds alter runoff characteristics, lower water table depths, and reduce the efficiency of riparian zones (Groffman et al., 2002). Several studies have investigated alternative methods to improve water quality in urban watersheds by incorporating urban forests or forested riparian zones into planning programs. Matteo et al. (2006) used watershed simulations to evaluate the effect of applying urban forestry best management practices (BMPs) to riparian and roadside buffer areas in an urbanizing watershed. Results from the study indicated that the selection and placement of tree species affect the ability of increased forest cover to reduce both sediment and nutrient loading. In addition to urban forestry BMPs, structural BMPs (e.g., dry ponds, constructed wetlands, bioretention systems, etc.) are frequently used in urban watersheds to reduce nutrient exports (NRC, 2000, 2008; Carey et al., 2012b). Nonstructural BMPs that emphasize preventative management (e.g., riparian buffers, zoning restrictions, educational programs, etc.) differ from structural BMPs that target pollutants in stormwater runoff. Factors such as initial stormwater concentrations influence variable nutrient removal efficiencies among common structural BMPs in urban watersheds (NRC, 2000; Carey et al., 2012b). Groffman and Crawford (2003) suggested that managing stormwater control structures and urban riparian areas to maximize soil moisture and organic matter content would restore NO3eN sinks. Restoration of degraded riparian zones requires careful attention to soil porosity and organic carbon levels to promote high microbial activity and low oxidation/reduction potential in groundwater (Correll, 2005). The assortment of urban nutrient sources, coupled with riparian zone degradation, directly affects relative retention in forested, agricultural, and urban watersheds. In Baltimore, Maryland, a forested watershed retained 95% of N inputs compared to 77% and 75% in agricultural and suburban watersheds, respectively (Groffman et al., 2004). The reported N retention in the suburban watershed may likely be much lower because only atmospheric and fertilizer inputs were included in nutrient calculations (Groffman et al., 2004). Castro et al. (2003) reported average atmospheric N retention for upland forests (92%) and agricultural areas (79%) along the U.S. Atlantic and Gulf Coast regions. In contrast, urban watersheds retained only 21e60% of TN inputs (Castro et al., 2003). Wollheim et al. (2005) also found greater retention in forested areas (93e97%) compared to urban areas (65e85%) in Massachusetts watersheds. Despite reduced overall N retention in urban watersheds, potential N retention in appropriately managed turfgrass can be significant. Groffman et al. (2009) suggested that similar carbon cycling rates in turfgrass and forests produce N sinks in soils that reduce NO3eN and nitrous oxide (N2O) losses. Raciti et al. (2008) described N cycling processes for lawns that can lead to greater atmospheric-N retention rates compared to forests. Agricultural soils, with depleted soil carbon levels relative to turfgrass, were also characterized by higher levels of soil NO3eN (Groffman et al., 2009). Understanding the capacity for long-term N retention in lawns, considering variables such as fertilizer management practices, soil characteristics, and climate, can provide further insight into urban nutrient cycling (Raciti et al., 2008). For example, climatic variability (e.g., drought conditions) can negatively affect N retention rates in agricultural and urban areas much more than R.O. Carey et al. / Environmental Pollution 173 (2013) 138e149 forested areas (Kaushal et al., 2008). Bijoor et al. (2008) also demonstrated that warmer temperatures can lead to increased N2O emissions from lawns. 6. Water quality impacts: harmful algal blooms In recent decades, there have been increased incidences of harmful algal blooms (HABs) e also called red or brown tides e that persist for increasing periods and cover larger areas in aquatic environments (NRC, 2000; Lapointe and Bedford, 2007; Heisler et al., 2008). Studies investigating the formation and persistence of near-shore and offshore HABs often do so within the context of cumulative pollution derived from nutrient sources in urban watersheds. Brand and Compton (2007) attributed the increased prevalence of HABs in Florida’s near-shore waters in the past five decades to population growth rates and land use disturbances, Bricker et al. (2008) linked recent blooms in several U.S. estuaries to population growth in coastal watersheds, and Heisler et al. (2008) described several examples where improved wastewater treatment reduced both the extent and occurrence of HABs. Urban populations are projected to increase in the future (United Nations, 2008), which suggests increased delivery of nutrients to aquatic systems. If sufficient nutrients are readily available and other growthlimiting conditions are satisfied, both non-toxic and toxic algae can increase in density to produce HABs. The decomposition of non-toxic macroalgal blooms leads to depleted dissolved oxygen levels, the loss of submerged aquatic vegetation, and damaged coral reefs. Toxic algal species additionally produce toxins that can be fatal to fish and other aquatic organisms; these toxins also contribute to neurological and respiratory problems in humans (Kirkpatrick et al., 2004; Abbott et al., 2009). Toxic cyanobacteria, the major class of freshwater HABs, produce cyanotoxins (e.g., microcystins and cylindrospermopsin) that can present multiple problems if ingested by humans (Abbott et al., 2009), thus disrupting recreational activities and threatening potable water resources (Dortch et al., 2008; Bigham et al., 2009; USEPA, 2009). These toxic cyanobacteria blooms can also be difficult to remove during water treatment (Westrick et al., 2010). Management concerns related to HABs therefore include both restoration of aquatic ecosystem productivity and protection of human health. Determining specific aspects of HABs has been particularly important in states with large coastal resources such as Florida, where all major groups of HABs, including those that cause red tides and poison fish, have occurred (Steidinger et al., 1999). Overall, 70 (50 marine and 20 freshwater) harmful algal species have been identified in Florida (Abbott et al., 2009). Karenia brevis (also known as Ptychodiscus brevis and Gymnodinium breve) is a dominant red tide species and its abundance along the southwestern coast of Florida has increased approximately 13e18 fold from 1954e1963 to 1994e2002 (Brand and Compton, 2007). Complete life cycle information and exact nutrient pathways for K. brevis are unknown (Brand and Compton, 2007). Using isotopic analyses of macroalgae, Barile (2004) investigated potential nutrient sources contributing to HABs in east-central Florida nearshore waters and reported that ambient concentrations of wastewater-derived N were sufficient to support K. brevis red tides. Lapointe and Bedford (2007) also used d15N values to link watershed nutrient sources to rhodophyte blooms in Lee County, Florida. Isotopic analysis of macroalgae indicated fertilizer-based N was primarily responsible for HABs in the wet season and wastewater sources supplied N in the dry season (Lapointe and Bedford, 2007). Lapointe et al. (2004) suggested both regional agricultural runoff and local wastewater discharges led to the subsequent development of HABs in the Florida Keys. 145 Nutrient enrichment as a result of human activities contributes to the increased prevalence of HABs, but the extent of this relationship and the effect of additional factors are unclear. Microcystin can occur in oligotrophic lakes and may be associated with seasonal fluctuations in water temperature (Bigham et al., 2009). Toxic blooms of K. brevis (Florida) and Alexandrium tamarense and A. catenella (northeastern and northwestern U.S.) can develop miles away from near-shore pollutant sources (Steidinger et al., 1999). In addition, a food web link between K. brevis and the cyanobacterium Trichodesmium in the Gulf of Mexico could stimulate the production of red tides. Lenes et al. (2001) and Walsh and Steidinger (2001) suggested that Saharan dust, transported in wind currents from Africa, provides the iron necessary for N fixation by Trichodesmium, and dissolved organic N (DON) excreted by the cyanobacterium serves as the N source for K. brevis. Nitrogen release rates (>50% of N fixed) from Trichodesmium in the form of DON and NH4eN may also be sufficient to support other phytoplankton species (Mulholland et al., 2004). Glibert et al. (2009) demonstrated through laboratory experiments that K. brevis can satisfy 40% of its cellular N requirements per hour by directly grazing on another cyanobacterium, Synechococcus. The ability of algal species to move toward nutrient sources, and the effect of climate variations, further complicate the process of identifying causative factors for HABs. Vertical migration (down to 90 m depths) of K. brevis allows this species to access subsurface NH4eN and urea (>20 m) transported from Mississippi River plumes in the northern Gulf of Mexico to the oligotrophic West Florida Shelf (WFS) (Stumpf et al., 2008). Therefore, local nutrient sources may not be the primary stimulus for the formation or persistence of high density HABs. Vargo et al. (2008) suggested a combination of sources could provide N and P necessary to sustain K. brevis blooms (up to18 months) in the WFS, including zooplankton excretion and fish remineralization. In 2004, Florida experienced numerous hurricanes and Hu et al. (2006) suggested that these events led to greater surface runoff and submarine groundwater discharges that stimulated intense red tides. Contributions from delayed submarine discharges may provide more nutrients than either riverine or atmospheric sources (Hu et al., 2006). Warmer temperatures may also promote the proliferation of toxic cyanobacteria blooms. Davis et al. (2009) collected samples from northeastern U.S. lakes and compared growth rates of toxic and non-toxic Microcystis using different experimental treatments. Elevated P concentrations, along with increased temperatures, produced the fastest overall growth rate for the toxic species (Davis et al., 2009). 7. Conclusions Optimizing watershed management practices to reduce nutrient losses remains a critical objective to improve urban water quality. Priority research areas include quantifying nutrient sources and sinks in urban watersheds, especially understudied aspects such as pet waste. Determining appropriate management strategies for urban vegetation such as green roofs and turfgrass will increase nutrient retention and limit exports. Turfgrass coverage is extensive in urban watersheds, but long-term nutrient cycling processes in these landscapes are not completely understood. Evaluating the fate of atmospheric N, particularly on turfgrass, may enhance current understanding of the relative significance of atmospheric deposits on landscape surfaces. Regulatory controls have reduced direct export of wastewater into receiving waters, but this export remains an important component of urban nutrient budgets. Both septic systems and WWTPs can discharge significant nutrient loads to receiving waters, depending on the efficiency and extent of wastewater treatment. Identifying the range of attenuation factors (e.g., 146 R.O. Carey et al. / Environmental Pollution 173 (2013) 138e149 dilution processes, nutrient transformations, etc.) associated with septic system discharges is critical to assessing the long-term capability of watersheds to assimilate nutrients from these sources. Furthermore, there is limited data available on the impact of long-term reclaimed water use on nutrient cycling in urban watersheds, especially considering variables such as nutrient concentrations in water used for irrigation, vegetative nutrient uptake efficiencies, and soil characteristics. Continuous in situ sensors of water quality parameters such as dissolved oxygen and temperature, and more recently, dissolved organic matter, NO3eN, and PO4, enhance the prospect of investigating multiple ecosystem processes simultaneously and can aid urban water quality research. Combining in situ sensors that provide high frequency measurements of water quality and other biogeochemical parameters with additional methods, such as isotopic analyses, can reveal both nutrient sources and mechanisms controlling nutrient cycling in urban watersheds. Improved assessment of nutrients in urban watersheds will help to advance our understanding of cultural eutrophication and the development of algal blooms. The various pathways by which algae can access nutrients and the processes that can either stimulate bloom formation or reduce the likelihood of their occurrence in different regions are unclear. Urban population projections suggest a greater potential for increased nutrient loads in the future, but adaptive watershed management requires targeted research on the range of factors contributing to degraded water quality. Acknowledgments This paper was written with financial support from Scotts Miracle-Gro, Marysville, Ohio, and from the University of Florida, Institute of Food and Agricultural Science. The University of New Hampshire Agricultural Experiment Station provided additional funding. We would also like to thank reviewers of this paper for their helpful suggestions and comments. 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