skip to main content


Title: Nitrification in a Subterranean Estuary: An Ex Situ and In Situ Method Comparison Determines Nitrate Is Available for Discharge
Abstract

Subterranean estuaries (STEs) form in the subsurface where fresh groundwater and seawater meet and mix. Subterranean estuaries support a variety of biogeochemical processes including those transforming nitrogen (N). Groundwater is often enriched with dissolved inorganic nitrogen (DIN), and transformations in the STE determine the fate of that DIN, which may be discharged to coastal waters. Nitrification oxidizes ammonium (NH4+) to nitrate, making DIN available for N removal via denitrification. We measured nitrification at an STE, in Virginia, USA using in situ and ex situ methods including conservative mixing models informed by in situ geochemical profiles, an in situ experiment with15NH4+tracer injection, and ex situ sediment slurry incubations with15NH4+tracer addition. All methods indicated nitrification in the STE, but the ex situ sediment slurries revealed higher rates than both the in situ tracr experiment and mixing model estimations. Nitrification rates ranged 55.0–183.16 μmol N m−2 d−1based on mixing models, 94.2–225 μmol N m−2 d−1in the in situ tracer experiment, and 36.6–109 μmol N m−2 d−1slurry incubations. The in situ tracer experiment revealed higher rates and spatial variation not captured by the other methods. The geochemical complexity of the STE makes it difficult to replicate in situ conditions with incubations and calculations based on chemical profiles integrate over longer timescales, therefore, in situ approaches may best quantify transformation rates. Our data suggest that STE nitrification produces NO3, altering the DIN pool discharged to overlying water via submarine groundwater discharge.

 
more » « less
NSF-PAR ID:
10513549
Author(s) / Creator(s):
 ;  ;  ;  
Publisher / Repository:
DOI PREFIX: 10.1029
Date Published:
Journal Name:
Journal of Geophysical Research: Biogeosciences
Volume:
129
Issue:
6
ISSN:
2169-8953
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Subterranean estuaries (STEs) form at the land‐sea boundary where groundwater and seawater mix. These biogeochemically reactive zones influence groundwater‐borne nutrient concentrations and speciation prior to export via submarine groundwater discharge (SGD). We examined a STE located along the York River Estuary (YRE) to determine if SGD delivers dissolved inorganic nitrogen (DIN) and phosphorus (DIP) to the overlying water. We assessed variations in STE geochemical profiles with depth across locations, times, and tidal stages, estimated N removal along the STE flow path, measured hydraulic gradients to estimate SGD, and calculated potential nutrient fluxes. Salinity, dissolved oxygen (DO), DIN, and DIP varied significantly with depth and season (p < 0.05), but not location or tidal stage. Ammonium dominated the DIN pool deep in the STE. Moving toward the sediment surface, ammonium concentrations decreased as nitrate and DO concentrations increased, suggesting nitrification. Potential sediment N removal rates mediated by denitrification were <8 mmoles N m−2 d−1. The total groundwater discharge rate was 38 ± 11 L m−2 d−1; discharge followed tidal and seasonal patterns. Net SGD nutrient fluxes were 0.065–3.2 and 0.019–0.093 mmoles m−2 d−1for DIN and DIP, respectively. However, microbial N removal in the STE may attenuate 0.58% to >100% of groundwater DIN. SGD fluxes were on the same order of magnitude as diffusive benthic fluxes but accounted for <10% of the nutrients delivered by fluvial advection in the YRE. Our results indicate the importance of STE biogeochemical transformations to SGD flux estimations and their role in coastal eutrophication and nutrient dynamics.

     
    more » « less
  2. Abstract

    Sandy sediment beaches covering 70% of non‐ice‐covered coastlines are important ecosystems for nutrient cycling along the land‐ocean continuum. Subterranean estuaries (STEs), where groundwater and seawater meet, are hotspots for biogeochemical cycling within sandy beaches. The STE microbial community facilitates biogeochemical reactions, determining the fate of nutrients, including nitrogen (N), supplied by groundwater. Nitrification influences the fate of N, oxidising reduced dissolved inorganic nitrogen (DIN), making it available for N removal. We used metabarcoding of 16S rRNA genes and quantitative PCR (qPCR) of ammonia monooxygenase (amoA) genes to characterise spatial and temporal variation in STE microbial community structure and nitrifying organisms. We examined nitrifier diversity, distribution and abundance to determine how geochemical measurements influenced their distribution in STEs. Sediment microbial communities varied with depth (p‐value = 0.001) and followed geochemical gradients in dissolved oxygen (DO), salinity, pH, dissolved inorganic carbon and DIN. Genetic potential for nitrification in the STE was evidenced by qPCR quantification ofamoAgenes. Ammonia oxidiser abundance was best explained by DIN, DO and pH. Our results suggest that geochemical gradients are tightly linked to STE community composition and nitrifier abundance, which are important to determine the fate and transport of groundwater‐derived nutrients to coastal waters.

     
    more » « less
  3. Abstract

    Terrestrial groundwater travels through subterranean estuaries before reaching the sea. Groundwater‐derived nutrients drive coastal water quality, primary production, and eutrophication. We determined how dissolved inorganic nitrogen (DIN), dissolved inorganic phosphorus (DIP), and dissolved organic nitrogen (DON) are transformed within subterranean estuaries and estimated submarine groundwater discharge (SGD) nutrient loads compiling > 10,000 groundwater samples from 216 sites worldwide. Nutrients exhibited complex, nonconservative behavior in subterranean estuaries. Fresh groundwater DIN and DIP are usually produced, and DON is consumed during transport. Median total SGD (saline and fresh) fluxes globally were 5.4, 2.6, and 0.18 Tmol yr−1for DIN, DON, and DIP, respectively. Despite large natural variability, total SGD fluxes likely exceed global riverine nutrient export. Fresh SGD is a small source of new nutrients, but saline SGD is an important source of mostly recycled nutrients. Nutrients exported via SGD via subterranean estuaries are critical to coastal biogeochemistry and a significant nutrient source to the oceans.

     
    more » « less
  4. Abstract

    To what extent multi-omic techniques could reflectin situmicrobial process rates remains unclear, especially for highly diverse habitats like soils. Here, we performed microcosm incubations using sandy soil from an agricultural site in Midwest USA. Microcosms amended with isotopically labeled ammonium and urea to simulate a fertilization event showed nitrification (up to 4.1 ± 0.87 µg N-NO3g−1dry soil d−1) and accumulation of N2O after 192 hours of incubation. Nitrification activity (NH4+ → NH2OH → NO → NO2- → NO3) was accompanied by a 6-fold increase in relative expression of the 16S rRNA gene (RNA/DNA) between 10 and 192 hours of incubation for ammonia-oxidizing bacteriaNitrosomonasandNitrosospira, unlike archaea and comammox bacteria, which showed stable gene expression. A strong relationship between nitrification activity and betaproteobacterial ammonia monooxygenase and nitrite oxidoreductase transcript abundances revealed that mRNA quantitatively reflected measured activity and was generally more sensitive than DNA under these conditions. Although peptides related to housekeeping proteins from nitrite-oxidizing microorganisms were detected, their abundance was not significantly correlated with activity, revealing that meta-proteomics provided only a qualitative assessment of activity. Altogether, these findings underscore the strengths and limitations of multi-omic approaches for assessing diverse microbial communities in soils and provide new insights into nitrification.

     
    more » « less
  5. Abstract

    Marine oxygen deficient zones are dynamic areas of microbial nitrogen cycling. Nitrification, the microbial oxidation of ammonia to nitrate, plays multiple roles in the biogeochemistry of these regions, including production of the greenhouse gas nitrous oxide (N2O). We present here the results of two oceanographic cruises investigating nitrification, nitrifying microorganisms, and N2O production and distribution from the offshore waters of the Eastern Tropical South Pacific. On each cruise, high‐resolution measurements of ammonium ([NH4+]), nitrite ([NO2]), and N2O were combined with15N tracer‐based determination of ammonia oxidation, nitrite oxidation, nitrate reduction, and N2O production rates. Depth‐integrated inventories of NH4+and NO2were positively correlated with one another and with depth‐integrated primary production. Depth‐integrated ammonia oxidation rates were correlated with sinking particulate organic nitrogen flux but not with primary production; ammonia oxidation rates were undetectable in trap‐collected sinking particulate material. Nitrite oxidation rates exceeded ammonia oxidation rates at most mesopelagic depths. We found positive correlations between archaealamoAgenes and ammonia oxidation rates and betweenNitrospina‐like 16S rRNA genes and nitrite oxidation rates. N2O concentrations in the upper oxycline reached values of >140 nM, even at the western extent of the cruise track, supporting air‐sea fluxes of up to 1.71 μmol m−2 day−1. Our results suggest that a source of NO2other than ammonia oxidation may fuel high rates of nitrite oxidation in the offshore Eastern Tropical South Pacific and that air‐sea fluxes of N2O from this region may be higher than previously estimated.

     
    more » « less