Habitat-specific distinctions in estuarine denitrification affect both ecosystem function and services

Resource limitation controls the base of food webs in many aquatic ecosystems. In coastal ecosystems, nitrogen (N) has been found to be the predominant limiting factor for primary producers. Due to the important role nitrogen plays in determining ecosystem function, understanding the processes that modulate its availability is critical. Shallow-water estuarine systems are highly heterogeneous. In temperate estuaries, multiple habitat types can exist in close proximity to one another, their distribution controlled primarily by physical energy, tidal elevation and geomorphology. Distinctions between these habitats such as rates of primary productivity and sediment characteristics likely affect material processing. We used membrane inlet mass spectrometry to measure changes in N2 flux (referred to here as denitrification) in multiple shallow-water estuarine habitats through an annual cycle. We found significantly higher rates of denitrification (DNF) in structured habitats such as submerged aquatic vegetation, salt marshes and oyster reefs than in intertidal and subtidal flats. Seasonal patterns were also observed, with higher DNF rates occurring in the warmer seasons. Additionally, there was an interaction between habitat type and season that we attributed to the seasonal patterns of enhanced productivity in individual habitat types. There was a strong correlation between denitrification and sediment oxygen demand (SOD) in all habitats and all seasons, suggesting the potential to utilize SOD to predict DNF. Denitrification efficiency was also higher in the structured habitats than in the flats. Nitrogen removal by these habitats was found to be an important contributor to estuarine ecosystem function. The ecosystem service of DNF in each habitat was evaluated in US dollars using rates from a regional nutrient-offset market to determine the cost to replace N through management efforts. Habitat-specific values of N removal ranged from approximately three thousand U.S. dollars per acre per year in the submerged aquatic vegetation to approximately four hundred U.S. dollars per acre per year in the subtidal flat. Because of the link between habitat type and processes such as DNF, changes in habitat area and distribution will have consequences for both ecosystem function and the delivery of ecosystem services

Nitrogen cycling processes within stormwater control measures: A review and call for research

Stormwater control measures (SCMs) have the potential to mitigate negative effects of watershed development on hydrology and water quality. Stormwater regulations and scientific literature have assumed that SCMs are important sites for denitrification, the permanent removal of nitrogen, but this assumption has been informed mainly by short-term loading studies and measurements of potential rates of nitrogen cycling. Recent research concluded that SCM nitrogen removal can be dominated by plant and soil assimilation rather than by denitrification, and rates of nitrogen fixation can exceed rates of denitrification in SCM sediments, resulting in a net addition of nitrogen. Nitrogen cycling measurements from other human-impacted aquatic habitats have presented similar results, additionally suggesting that dissimilatory nitrate reduction to ammonium (DNRA) and algal uptake could be important processes for recycling nitrogen in SCMs. Future research should directly measure a suite of nitrogen cycling processes in SCMs and reveal controlling mechanisms of individual rate processes. There is ample opportunity for research on SCM nitrogen cycling, including investigations of seasonal variation, differences between climatic regions, and trade-offs between nitrogen removal and phosphorus removal. Understanding nitrogen dynamics within SCMs will inform more efficient SCM design and management that promotes denitrification to help mitigate negative effects of urban stormwater on downstream ecosystems

Living shorelines enhance nitrogen removal capacity over time

Living shorelines are nature-based solutions to coastal erosion that can be constructed as salt marshes with fringing oyster reefs. Each of these habitats can decrease the potential for eutrophication through increased nitrogen (N) removal via denitrification. However, the development of N cycling over time has not been studied in living shorelines. This research measured denitrification rates in a chronosequence of living shorelines spanning 0–20 years in age in Bogue Sound, NC. Analyses were conducted seasonally from summer 2014 to spring 2015 along an elevation transect through the salt marsh, oyster reef, and adjacent sandflat at all sites. Gas fluxes (N2 and O2) from sediment core incubations were measured with a membrane inlet mass spectrometer (MIMS) to assess denitrification and sediment oxygen demand. Fluxes of dissolved nutrients and the greenhouse gas N2O were measured. Sediment properties, inundation frequency, oyster filtration rates, and marsh grass stem density were also quantified. There was no significant difference in denitrification rates among habitats. N removal consistently increased from the 0- to 7-year-old sites. Denitrification efficiency was always greater than 50% and positive N2O fluxes were negligible. Our results suggest that living shorelines increase net N removal within a relatively short time period following construction, without introducing deleterious greenhouse gas emissions. This demonstrates that living shorelines can play an important role in estuarine N cycling and management

Coastal stormwater wet pond sediment nitrogen dynamics

Wet ponds are a common type of stormwater control measure (SCM) in coastal areas of the southeastern US, but their internal nitrogen dynamics have not been extensively studied. Using flow-through intact sediment core incubations, net sediment N2 fluxes before and after a nitrate addition from five wet ponds spanning a range of ages (3.25–10 years old) were quantified through membrane inlet mass spectrometry during early summer. Multiple locations within a single wet pond (6.16 years old) were also sampled during ambient conditions in late summer to determine the combined effects of depth, vegetation, and flow path position on net N2 fluxes at the sediment-water interface. All pond sediments had considerable rates of net nitrogen fixation during ambient conditions, and net N2 fluxes during nitrate-enriched conditions were significantly correlated with pond age. Following a nitrate addition to simulate storm conditions, younger pond sediments shifted towards net denitrification, but older ponds exhibited even higher rates of net nitrogen fixation. The pond forebay had significantly higher rates of net nitrogen fixation compared to the main basin, and rates throughout the pond were an order of magnitude higher than the early summer experiment. These results identify less than optimal nitrogen processing in this common SCM, however, data presented here suggest that water column mixing and pond sediment excavation could improve the capacity of wet ponds to enhance water quality by permanently removing nitrogen

Biological activity exceeds biogenic structure in influencing sediment nitrogen cycling in experimental oyster reefs

Oysters are estuarine ecosystem engineers, in that their physical structure and biological function affect ecosystem processes such as organic matter and nutrient cycling. Oysters deliver material to the sediments through biodeposition and sedimentation caused by modification of flow around the reef. We conducted an experiment to distinguish between biotic effects and physical structure of oyster reefs on sediment nitrogen cycling. Experimental reefs consisting of live oysters, oyster shells alone and mudflats (controls) were sampled for a period of 4 wk for sediment organic matter, C and N content and fluxes of nitrogen (NH4+, NOX and N2) and oxygen (O2). We hypothesized that the biological activity of the oyster would deposit more, higher quality organic matter compared to deposition from flow modification alone, thus facilitating denitrification and having a larger impact on sediment nitrogen cycling. Compared to the controls, the live oyster experimental reefs increased sediment denitrification by 61% and the shell experimental reefs showed a 24% increase. The live oyster experimental reef also had the largest O2 demand and NH4+ production. Reef structure likely increased organic matter deposition, but the higher quality and larger quantity of organic matter associated with live oysters increased denitrification and microbial respiration. This experiment shows that the ecosystem service of nitrogen removal provided by oysters is primarily driven by the biological function of the oysters and secondarily from the physical structure of the reef. Our increased understanding of how oysters engineer ecosystems and modify nutrient cycling can help guide future oyster restoration efforts

The Effects of Urbanization and Retention-Based Stormwater Management on Coastal Plain Stream Nutrient Export

Stormwater nutrient pollution can be more effectively managed if there is a predictable link between urbanization and pollutant export. The goal of this study was to determine the effects of increased watershed impervious surface cover (ISC) and retention-based stormwater management on stream discharge and nutrient export from coastal plain streams in the southeastern United States. To quantify coastal plain stream nutrient export, measurements of stream discharge and concentrations of dissolved nutrients, particulate nitrogen, and algal biomass (as chlorophyll a) were collected during baseflow and stormflow for four years from five streams on Marine Corps Base Camp Lejeune near Jacksonville, North Carolina. The study streams had watersheds that spanned a range of ISC (1–38%) and included an urban watershed drained extensively by stormwater ponds. Urban streams had higher rates of annual discharge than less impacted streams due to elevated discharge at all rates of flow, more cumulative discharge at high flows, and dampened seasonal patterns. Streams with higher watershed ISC had higher rates of annual export of all measured nutrients due to increased stream discharge and concentrations of inorganic and particulate nitrogen. The relative importance of dissolved organic nitrogen decreased with watershed ISC, but it was still the dominant form of nitrogen export in every study stream except the stream that was dominated by particulate nitrogen export from stormwater pond algal production. Based on these findings, this study suggests that stormwater management emphasizing stormwater harvesting and evapotranspiration, increased wetland area, and decreased anthropogenic nutrient sources could reduce nutrient export from urban coastal plain streams

Seasonal Variation in Nitrate Removal Mechanisms in Coastal Stormwater Ponds

Stormwater wet ponds (SWPs) are engineered structures used to collect and retain stormwater runoff from developed areas. SWPs are generally regarded as important nitrogen (N) sinks, but seasonal variation in SWP N cycling that influences pond nitrogen removal has not been characterized. To inform SWP function across seasons, we sampled the sediments and water columns of three stormwater ponds in the southeastern US coastal plain and measured gas and nutrient fluxes from the sediment-water interface during ambient conditions and nitrate (NO3)-enriched “simulated storm” conditions. Dissolved organic nitrogen (DON) was the dominant form of dissolved N in the water column, while nitrate + nitrite (NOx) was typically below detection. SWP sediment organic matter properties varied by study site but had minimal impact on sediment N processes or estimated NO3 fate. SWP sediments generally functioned as TN sinks during NO3-enriched conditions, but the estimated fate of NO3 varied based on water temperature, DON concentrations, and sediment O2 uptake. These results suggest that permanent N removal (denitrification) by SWPs varies seasonally, with retention of NOx becoming more important during hotter conditions when NOx uptake is largest. Low ambient NOx concentrations and rapid NO3 uptake suggest that coastal stormwater ponds can host reduced conditions that may promote NO3 retention over denitrification. Additional research is needed to determine the fate of retained NO3 in SWP sediments and how variation in NO3 fate might impact downstream water quality

Water quality before and after watershed-scale implementation of stormwater wet ponds in the coastal plain

Wet ponds have been used extensively for stormwater control throughout the US, including coastal areas. Despite the widespread application of these water control structures, few studies have investigated how watershed-scale implementation of wet ponds affects downstream water quality or how the pollutant removal efficacy of wet ponds changes over time in a coastal setting. This study utilizes a seven year data set of nutrient, total suspended solid, and chlorophyll-a concentration data collected during baseflow and stormflow from two coastal headwater streams draining a developed (28% impervious) and an undeveloped (1.2% impervious) watershed. The seven year record encompasses before, during, and after a large construction project and concurrent implementation of wet ponds in the developed watershed that drain 97% of the watershed area. Additional nutrient, total suspended solid, and chlorophyll-a concentration data were collected from within a wet pond in the developed watershed during baseflow over a single spring and summer. A comparison of stream water quality before and after the construction project and wet pond implementation in the developed watershed showed that mean chlorophyll-a, nitrate-nitrite (NOx−), organic nitrogen, and total suspended solid concentrations significantly increased, the mean orthophosphate (PO43−) concentration significantly decreased, and the mean ammonium (NH4+) concentration did not change. Over a three year time period after construction and pond implementation, developed stream chlorophyll-a, ammonium, and organic nitrogen concentrations decreased, and nitrate-nitrite, orthophosphate, and total suspended solid concentrations increased compared to the reference stream during the same period, indicating changes in pollutant removal capacity. A comparison of baseflow and stormflow samples during the Post period and samples from a wet pond in the developed watershed indicated that ponds were functioning as sources of chlorophyll-a and total suspended solids to the stream and sinks for nitrate-nitrite. Overall, watershed-scale implementation of wet ponds in the developed watershed failed to mitigate many negative water quality impacts caused by increased development. This study suggests that centralized stormwater management may not be optimal for maintaining water quality in coastal environments, and that pond retrofits combined with frequent excavation could improve pollutant removal by wet ponds. Further research on the effects of nutrient cycling in coastal wet ponds and wet pond maintenance is needed

Non-Native Marsh Grass (Phragmites australis) Enhances Both Storm and Ambient Nitrogen Removal Capacity in Marine Systems

Marshes play a key role in global nitrogen cycling at the land–water margin. Invasive species are generally considered detrimental as they alter ecosystems they invade, but recent studies have shown some established invasive species can enhance certain ecosystem functions. The European haplotype of Phragmites australis is an aggressive and widespread invasive plant species in North America. We hypothesized that P. australis may play an important role in marsh nitrogen cycling by promoting higher rates of sediment denitrification compared with native marsh species. Seasonal measurements of sediment dissolved gas (N2 and O2) fluxes at three sites within the Albemarle-Pamlico Region of North Carolina compared sediments from invasive P. australis, native Spartina alterniflora, and/or Juncus roemarianus, and unvegetated sediments. In a marine tidal site, annual net denitrification in sediments associated with upland P. australis was highest compared to lower elevation marsh species or unvegetated sediments under ambient (139 μmol N2-N m−2 h−1) and nitrate enriched (219 μmol N2-N m−2 h−1) conditions. N2 fluxes were lower in sediments from two brackish marshes and did not differ between associated species, unvegetated sediments, or between high or low organic matter sites. Treatments with elevated nitrate showed enhanced net denitrification in most sediments at the marine site, suggesting the capacity to remove additional nitrate delivered episodically. Additionally, N2 fluxes measured before and after Hurricane Florence showed an increase in denitrification in P. australis sediments after the hurricane. Ecosystem value for this nitrogen removal service in the marine tidal site was estimated at US$ 266–426 *ha−1*yr−1. These results demonstrate an important role for invasive P. australis in coastal nitrogen cycling in marine environments and provide landscape context for potential biogeochemical impacts of this invasion

Spatiotemporal patterns in the export of dissolved organic carbon and chromophoric dissolved organic matter from a coastal, blackwater river

We examined seasonal and spatial patterns in dissolved organic carbon (DOC) and chromophoric dissolved organic matter (CDOM) in the Chowan River watershed, North Carolina, a blackwater river which discharges into the second largest estuary in the United States, the Albemarle–Pamlico Estuarine System. From April 2008 to May 2010, DOC concentration did not significantly vary across seasons (range 7.69–30.39 mg L−1); however, CDOM molecular size and aromaticity increased throughout the spring, decreased during the summer and fall, and remained relatively low in the winter. Spectral slope ratios suggested microbial processing of CDOM in the spring and photodegradation of CDOM in the summer and fall. Spatially, DOC and CDOM concentrations were similar in the mainstem and at the mouths of two tributaries, Bennetts Creek and Wiccacon River, but were significantly higher upstream on the tributaries. DOC concentration was positively correlated with CDOM absorbance coefficients at 254 and 350 nm; however, these optical proxies explained only ~60 % of the variance. DOC and CDOM absorption loads to the Albemarle Sound ranged from 2.63 × 1010 g year−1 and 9.84 × 1010 m2 year−1, respectively, in a dry year and 7.9 × 1010 g year−1 and 2.2 × 1011 m2 year−1, respectively, in a wet year, which are comparable to non-blackwater rivers with larger watersheds. Blackwater rivers may therefore represent “hotspots” in coastal carbon chemistry, with seasonal variations in the quality and quantity of DOC and CDOM influencing estuarine food web dynamics and net ecosystem metabolism