Variation in sediment and seagrass characteristics reflect multiple stressors along a nitrogen-enrichment gradient in a New England lagoon

© The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Haviland, K. A., Howarth, R. W., Marino, R., & Hayn, M. Variation in sediment and seagrass characteristics reflect multiple stressors along a nitrogen-enrichment gradient in a New England lagoon. Limnology and Oceanography, 67, (2022): 660-667, https://doi.org/10.1002/lno.12025.We examined concentrations of organic carbon, dissolved sulfides, total sediment sulfur, and stable sulfur isotope ratios in seagrass leaf tissues across a nitrogen-enrichment gradient in a coastal marine ecosystem (Cape Cod, Massachusetts) in 2007–2010 and 2017–2019. We also measured seagrass aboveground and belowground biomass, epibiota biomass, and leaf chlorophyll content. Seagrasses were present at all sites in the former period but were lost at our most nitrogen-impacted site (Snug Harbor) by 2011. In 2007–2010, sediment organic carbon and dissolved sulfides were highest in Snug Harbor and decreased along the gradient; leaf tissues depleted in 34S also indicated higher sulfide intrusion into seagrass tissues in more eutrophic areas. By 2017–2019, sediment organic carbon and pore-water soluble sulfides had decreased in Snug Harbor, but had increased at the intermediate site, to levels found at the most impacted site prior to the seagrass die-off. Again, leaf tissue 34S depletion reflected this pattern, indicating seagrasses were exposed to the highest sulfides at the intermediate site. The decreases in sediment organic carbon and soluble sulfides in Snug Harbor years after the loss of the seagrasses illustrate a feedback between high organic matter in seagrass beds and increasing stressors like elevated soluble sulfides in nutrient-enriched systems. We found significant relationships between sediment conditions and seagrass responses, including greater aboveground to belowground biomass ratios, epibiota biomass, and 34S-depleted leaves at sites with high pore-water sulfide and highly organic sediments. Our research suggests that the reduction of anthropogenic nitrogen entering the harbor is necessary for improving sediment quality and preventing seagrass mortality.The authors thankfully acknowledge as our funding sources: The National Science Foundation Biocomplexity, GRFP, and LTREB programs (grants 0420575, 1654845, and 2018241438), and the Woods Hole SeaGrant program

Role of external inputs of nutrients to aquatic ecosystems in determining prevalence of nitrogen vs. phosphorus limitation of net primary productivity

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Howarth, R. W., Chan, F., Swaney, D. P., Marino, R. M., & Hayn, M. Role of external inputs of nutrients to aquatic ecosystems in determining prevalence of nitrogen vs. phosphorus limitation of net primary productivity. Biogeochemistry, (2021), https://doi.org/10.1007/s10533-021-00765-z.Whether net primary productivity in an aquatic ecosystem is limited by nitrogen (N), limited by phosphorus (P), or co-limited by N & P is determined by the relative supply of N and P to phytoplankton compared to their elemental requirements for primary production, often characterized by the “Redfield” ratio. The supply of these essential nutrients is affected by both external inputs and biogeochemical processes within the ecosystem. In this paper, we examine external sources of nutrients to aquatic systems and how the balance of N to P inputs influences nutrient limitation. For ocean subtropical gyres, a relatively balanced input of N and P relative to the Redfield ratio from deep ocean sources often leads to near co-limitation by N and P. For lakes, the external nutrient inputs come largely from watershed sources, and we demonstrate that on average the N:P ratio for these inputs across the United States is well above that needed by phytoplankton, which may contribute to P limitation in those lake that experience this average nutrient loading. Watershed inputs are also important for estuaries and coastal marine ecosystems, but ocean sources of nutrients are also significant contributors to overall nutrient loads. The ocean-nutrient sources of N and P are very often at or below the Redfield ratio of 16:1 molar, and can be substantially so, particularly in areas where the continental shelf is wide. This large input of coastal ocean nutrients with a low N:P ratio is one factor that may make N limitation more likely in many coastal marine ecosystems than in lakes.Preparation of this manuscript was supported by a National Science Foundation Grant # 1654845 from the Long Term Research in Environmental Biology program, a grant from the Atkinson Center for a Sustainable Future at Cornell University, and by an endowment given to Cornell by David R. Atkinson to support a professorship held by RWH

Tidal and groundwater fluxes to a shallow, microtidal estuary : constraining inputs through field observations and hydrodynamic modeling

This paper is not subject to U.S. copyright. The definitive version was published in Estuaries and Coasts 35 (2012): 1285-1298, doi:10.1007/s12237-012-9515-x.Increased nutrient loading to estuaries has led to eutrophication, degraded water quality, and ecological transformations. Quantifying nutrient loads in systems with significant groundwater input can be difficult due to the challenge of measuring groundwater fluxes. We quantified tidal and freshwater fluxes over an 8-week period at the entrance of West Falmouth Harbor, Massachusetts, a eutrophic, groundwater-fed estuary. Fluxes were estimated from velocity and salinity measurements and a total exchange flow (TEF) methodology. Intermittent cross-sectional measurements of velocity and salinity were used to convert point measurements to cross-sectionally averaged values over the entire deployment (index relationships). The estimated mean freshwater flux (0.19 m3/s) for the 8-week period was mainly due to groundwater input (0.21 m3/s) with contributions from precipitation to the estuary surface (0.026 m3/s) and removal by evaporation (0.048 m3/s). Spring–neap variations in freshwater export that appeared in shorter-term averages were mostly artifacts of the index relationships. Hydrodynamic modeling with steady groundwater input demonstrated that while the TEF methodology resolves the freshwater flux signal, calibration of the index– salinity relationships during spring tide conditions only was responsible for most of the spring–neap signal. The mean freshwater flux over the entire period estimated from the combination of the index-velocity, index–salinity, and TEF calculations were consistent with the model, suggesting that this methodology is a reliable way of estimating freshwater fluxes in the estuary over timescales greater than the spring– neap cycle. Combining this type of field campaign with hydrodynamic modeling provides guidance for estimating both magnitude of groundwater input and estuarine storage of freshwater and sets the stage for robust estimation of the nutrient load in groundwater.Funding was provided by the USGS Coastal and Marine Geology Program and by National Science Foundation Award #0420575 from the Biocomplexity/Coupled Biogeochemical Cycles Program

Chemical order and local structure of the lead-free relaxor ferroelectric Na1/2Bi1/2TiO3

The A-site mixed perovskite sodium bismuth titanate (Na1/2Bi1/2)TiO3 (NBT) is investigated by means of first-principles calculations based on density functional theory. By studying different geometries with varying occupations of the A-site, the influence of chemical order on the thermodynamic stability and local structure is explored. We find that the hybridization of Bi 6sp with O 2p-states leads to stereochemically active Bi3+ lone pairs and increases the stability of structures with high Bi concentrations in {001}-planes. This goes along with displacive disorder on the oxygen sublattice, which up to now has been neglected in experimental studies. The calculated ordering energies are, however, small as compared to the thermal energy and therefore only short-range chemical order can be expected in experiments. Thus, it is conceivable that chemically ordered local areas can act as nucleation sites for polar nano-regions, which would explain the experimentally observed relaxor behavior of NBT

Chemical order and local structure of the lead-free relaxor ferroelectric (Na1/2Bi1/2)TiO3

The A-site mixed perovskite sodium bismuth titanate (Na1/2Bi1/2)TiO3 (NBT) is investigated by means of first-principles calculations based on density functional theory. By studying different geometries with varying occupations of the A-site, the influence of chemical order on the thermodynamic stability and local structure is explored. We find that the hybridization of Bi 6sp with O 2p-states leads to stereochemically active Bi3+ lone pairs and increases the stability of structures with high Bi concentrations in {001}-planes. This goes along with displacive disorder on the oxygen sublattice, which up to now has been neglected in experimental studies. The calculated ordering energies are, however, small as compared to the thermal energy and therefore only short-range chemical order can be expected in experiments. Thus, it is conceivable that chemically ordered local areas can act as nucleation sites for polar nano-regions, which would explain the experimentally observed relaxor behavior of NBT

A-site occupancy in the lead-free (Bi1/2Na1/2TiO3)0.94-(BaTiO3)0.06 piezoceramic : combining first-principles study and TEM

The crystal structure of the lead-free piezoelectric ceramic(Bi1/2Na1/2TiO3)0.94–(BaTiO3)0.06 was investigated by first-principles calculations and high-resolution transmission electron microscopy(HRTEM) imaging. Structures with different A-site occupation were relaxed by total energy calculations within density functional theory and then used for simulating the corresponding HRTEM images. Simulated and experimental HRTEM images were compared and the closest match selected for structure interpretation. By combining these techniques, we have identified the Bi(Ba)/Na distribution on the A-site to be homogeneous. We exclude the possibility that regions visible in HRTEM images within one grain can be attributed to different ordering but to a slight tilting of the structure with respect to the electron beam

A-site occupancy in the lead-free (Bi1/2Na1/2TiO3)0.94–(BaTiO3)0.06 piezoceramic: Combining first-principles study and TEM

The crystal structure of the lead-free piezoelectric ceramic (Bi1/2Na1/2TiO3)0.94–(BaTiO3)0.06 was investigated by first-principles calculations and high-resolution transmission electron microscopy (HRTEM) imaging. Structures with different A-site occupation were relaxed by total energy calculations within density functional theory and then used for simulating the corresponding HRTEM images. Simulated and experimental HRTEM images were compared and the closest match selected for structure interpretation. By combining these techniques, we have identified the Bi(Ba)/Na distribution on the A-site to be homogeneous. We exclude the possibility that regions visible in HRTEM images within one grain can be attributed to different ordering but to a slight tilting of the structure with respect to the electron beam

Prostate cancer navigation: initial experience and association with time to care.

OBJECTIVE: To evaluate factors associated with use of patient navigation in a prostate cancer population and identify whether navigation is associated with prolonged time to care. Cancer patient navigation has been shown to improve access to cancer screening, diagnosis, and treatment, but little is known about patient navigation in prostate cancer care. METHODS: All men diagnosed with localized prostate cancer between 2009 and 2015 were abstracted from the MaineHealth multi-specialty tumor registry. Regression analyses controlling for patient-, disease-, and system-level factors evaluated characteristics associated with navigation utilization. The association between navigation utilization, barriers to care, and longer time to treatment was assessed with Cox proportional hazards regression. RESULTS: Of the patient population (n = 1587), 85% of men were navigated. Navigation use was associated with earlier year of diagnosis, treatment by a high-volume urologist, and lower risk disease (p \u3c 0.05). Treatment delay was associated with low-risk disease (vs: intermediate OR 0.62, 95% CI 0.46-0.85 and high OR 0.16, 95% CI 0.1-0.25) and receipt of navigation services (OR 1.65, 95% CI 1.12-2.45) but not distance to care, insurance, or treatment choice. CONCLUSIONS: We observed that patients with low-risk prostate cancer were more likely to utilize navigation, but traditional barriers to care were not associated with utilization. Navigation was associated with longer time to treatment, which likely reflects clinically appropriate delays associated with greater shared decision making. Time to treatment may not be the ideal metric for evaluating navigation in prostate cancer; shared decision making, patient satisfaction, and psychosocial outcomes may be more appropriate