Seasonality of nitrogen sources, cycling, and loading in a New England river discerned from nitrate isotope ratios

Coastal waters globally are increasingly impacted due to the anthropogenic loading of nitrogen (N) from the watershed. To assess dominant sources contributing to the eutrophication of the Little Narragansett Bay estuary in New England, we carried out an annual study of N loading from the Pawcatuck River. We conducted weekly monitoring of nutrients and nitrate (NO3-) isotope ratios (15N / 14N, 18O / 16O, and 17O / 16O) at the mouth of the river and from the larger of two wastewater treatment facilities (WWTFs) along the estuary, as well as seasonal along-river surveys. Our observations reveal a direct relationship between N loading and the magnitude of river discharge and a consequent seasonality to N loading into the estuary – rendering loading from the WWTFs and from an industrial site more important at lower river flows during warmer months, comprising ∼ 23 % and ∼ 18 % of N loading, respectively. Riverine nutrients derived predominantly from deeper groundwater and the industrial point source upriver in summer and from shallower groundwater and surface flow during colder months – wherein NO3- associated with deeper groundwater had higher 15N / 14N ratios than shallower groundwater. Corresponding NO3- 18O / 16O ratios were lower during the warm season, due to increased biological cycling in-river. Uncycled atmospheric NO3-, detected from its unique mass-independent NO3- 17O / 16O vs. 18O / 16O fractionation, accounted for < 3 % of riverine NO3-, even at elevated discharge. Along-river, NO3- 15N / 14N ratios showed a correspondence to regional land use, increasing from agricultural and forested catchments to the more urbanized watershed downriver. The evolution of 18O / 16O isotope ratios along-river conformed to the notion of nutrient spiraling, reflecting the input of NO3- from the catchment and from in-river nitrification and its coincident removal by biological consumption. These findings stress the importance of considering seasonality of riverine N sources and loading to mitigate eutrophication in receiving estuaries. Our study further advances a conceptual framework that reconciles with the current theory of riverine nutrient cycling, from which to robustly interpret NO3- isotope ratios to constrain cycling and source partitioning in river systems.

Barium stable isotopes as a fingerprint of biological cycling in the Amazon River basin

The biological cycle of rock-derived nutrients on the continents is a major component of element transfer between the Earth's surface compartments, but its magnitude currently remains elusive. The use of the stable isotope composition of rock-derived nutrients, which can be fractionated during biological uptake, provides a promising path forward with respect to quantifying biological cycling and its overall contribution to global element cycling. In this paper, we rely on the nutrient-like behaviour of the trace element barium (Ba) and use its elemental and stable isotope compositions in dissolved and sediment load river samples to investigate biological cycling in the Amazon Basin. From these measurements, we show that dissolved Ba mainly derives from silicate rocks, and a correlation between dissolved Ba and K abundances suggests that biological cycling plays a role in the Ba river budget. Furthermore, the isotope composition of Ba (δ138Ba) in the dissolved load was found to be significantly different from that of the parent silicate rocks, implying that dissolved Ba isotopic signatures are affected by (i) the precipitation of soil-forming secondary phases as well as (ii) biological uptake and release from dead organic matter. Results from an isotope mass balance method applied to the river dissolved load data indicate that, after its release to solution by rock weathering, Ba is partitioned between the river dissolved load, secondary weathering products (such as those found in soils and river sediments), and the biota. In most sub-catchments of the Amazon, river Ba abundances and isotope compositions are significantly affected by biological cycling. Relationships between estimates of Ba cycled through biota and independent metrics of ecosystem dynamics (such as gross primary production and terrestrial ecosystem respiration) allow us to discuss the role of environmental parameters such as climate or erosion rates on the biological cycling of Ba and, by extension, the role of major rock-derived nutrients. In addition, catchment-scale mass and isotope budgets of Ba show that the measured riverine export of Ba is lower than the estimated delivery of Ba to the Earth surface through rock alteration. This indicates the existence of a missing Ba component, which we attribute to the formation of Ba-bearing particulate organics (possibly accumulating as soil organic matter or currently growing biomass within the catchments) and to organic-bound Ba exported as “unsampled” river particulate organic matter. Given our findings on the trace element Ba, we explore whether the river fluxes of most major rock-derived nutrients (K, Mg, Ca) might also be significantly affected by biological uptake or release. A first-order correction of river-derived silicate weathering fluxes from biological cycling shows that the carbon dioxide (CO2) consumption by silicate weathering at the mouth of the Amazon could be several times higher than the previously reported value of 13 × 109 mol CO2 yr−1 (Gaillardet et al., 1997). Overall, our study clearly shows that the chemical and isotope compositions of rivers in the Amazon – and most likely in other large river basins – bear a biological imprint, thereby challenging common assumptions made in weathering studies.

Sources and cycling of nitrogen in a New England river discerned from nitrate isotope ratios

Coastal waters globally are increasingly impacted due to the anthropogenic loading of nitrogen (N) from the watershed. In order to assess dominant sources of N contributing to the eutrophication of the Little Narragansett Bay estuary in New England, we carried out an annual study of N loading from the Pawcatuck River. We conducted weekly monitoring of nutrients and nitrate (NO3−) isotope ratios (15N / 14N, 18O / 16O and 17O / 16O) at the mouth of the river and from the larger of two Waste Water Treatment Facilities (WWTFs) along the estuary, as well as seasonal along-river surveys. Our observations reveal a direct relationship between N loading and the magnitude of river discharge, and a consequent seasonality to N loading into the estuary – rendering loading from the WWTFs and from an industrial site upriver more important at lower river flows during warmer months, comprising ~23 % and ~18 % of N loading, respectively. Riverine nutrients derived predominantly from deeper groundwater and the industrial point source upriver during low base flow in summer, and from shallower groundwater and surface flow at higher river flows during colder months. Loading of dissolved organic nitrogen appeared to increase with river discharge, ostensibly delivered by surface water. The NO3− associated with deeper groundwater had higher 15N / 14N ratios than shallower groundwater, consistent with the expectation fractionation due to partial denitrification. Along-river, NO3− 15N / 14N ratios showed a correspondence to regional land use, increasing from agricultural and forested catchments to the more urbanized watershed downriver, with the agricultural and urbanized portions of the watershed contributing disproportionately to total N loading. Corresponding NO3− 18O / 16O ratios were lower during the warm season, a dynamic that we ascribe to increased biological cycling in-river. The 18O / 16O isotope ratios along-river were consistent with the notion of nutrient spiraling, reflecting NO3− input from the watershed and in-river nitrification and its coincident removal by biological consumption. Uncycled atmospheric NO3−, detected from its unique mass-independent NO3− 17O / 16O vs. 18O / 16O fractionation, accounted for

Biogeochemical cycling of phosphorus in subsoils of temperate forest ecosystems

Tree roots penetrate the soil to several meters depth, but the role of subsoils for the supply of nutrient elements such as phosphorus (P) to the trees is poorly understood. Here, we tested the hypothesis that increased P deficiency in the topsoil results in an increased microbial recycling of P from the forest subsoil. We sampled soils from four German temperate forest sites representing a gradient in total P stocks. We analyzed the oxygen isotopic composition of HCl-extractable phosphate (δ18OP) and identified differences in P speciation with increasing soil depth using X-ray absorption near-edge structure (XANES) spectroscopy. We further determined microbial oxygen demand with and without nutrient supply at different soil depths to analyse nutrient limitation of microbial growth and used nanoscale secondary ion mass spectrometry (NanoSIMS) to visualize spatial P gradients in the rhizosphere. We found that δ18OP values in the topsoil of all sites were close to the isotopic signal imparted by biological cycling when oxygen isotopes in phosphate are exchanged by enzymatic activity. However, with increasing soil depth and increasing HCl-P concentrations, δ18Ο values continuously decreased towards values expected for primary minerals in parent material at depths below 60 cm at sites with high subsoil P stocks and below more than 2 m at sites with low subsoil P stocks, respectively. For these depths, XANES spectra also indicated the presence of apatite. NanoSIMS images showed an enrichment of P in the rhizosphere in the topsoil of a site with high P stocks, while this P enrichment was absent at a site with low P stocks and in both subsoils. Addition of C, N and P alone or in combination revealed that microbial activity in subsoils of sites with low P stocks was mostly P limited, whereas sites with high P stocks indicated N limitation or N and P co-limitation. We conclude that subsoil P resources are recycled by trees and soil microorganisms. With continued weathering of the bedrock and mobilisation of P from the weathered rocks, P cycling will proceed to greater depths, especially at sites characterised by P limitation.

Barium stable isotopes as a fingerprint of biological cycling in the Amazon River Basin

Although biological cycling of rock-derived nutrients is a major operator of element cycles at the Earth surface, its magnitude still remains elusive. The isotope composition of rock-derived nutrients, which can be fractionated during biological uptake, is a powerful tool to quantify biological cycling. In this paper we use the elemental and isotopic composition of such a rock-derived nutrient, the trace element barium (Ba), measured in river dissolved and sediment load samples collected across the Amazon Basin. We show that dissolved Ba derives mainly from silicate rocks, while a correlation between dissolved Ba and K abundances suggests a strong role of biological cycling on the Ba river budget. The isotope composition of Ba (δ138Ba) of the dissolved load is significantly different from that of silicate rocks and is affected by i) formation of secondary phases and ii) biological uptake and release from dead organic matter. Results from an isotope mass balance model applied to the river dissolved load data indicate that after its release to solution by rock weathering, Ba is partitioned between the dissolved load, the secondary weathering products such as those found in soils and river sediments, and the biota. In most sub-catchments of the Amazon, river dissolved Ba abundance and isotope composition are significantly affected by biological cycling. Relationships between estimates of Ba cycling and independent metrics of ecosystem dynamics (such as Gross Primary Production and Terrestrial Ecosystem Respiration) allows us to discuss the role of erosion rates on the cycling of rock-derived nutrients. In addition, river catchment-scale mass and isotope budgets of Ba show that the measured riverine export of Ba is lower than the estimated delivery of Ba to the Earth surface through rock alteration. This indicates the existence of a missing Ba component, that we attribute to the formation of a Ba-bearing particulate organic component, possibly accumulating as soil organic matter or currently growing biomass within the catchments; and to organic-bound exported as unsampled river particulate organic matter. Given our findings on the minor nutrient Ba, we explore whether the river fluxes of most major rock-derived nutrients (K, Mg, Ca) might also be significantly affected by biological uptake or release. A first-order correction of river-derived silicate weathering fluxes from biological cycling shows that, at the Amazon at mouth, the CO2 consumption by silicate weathering should be 20 % higher than the yet-reported value. Overall, our study clearly shows that the chemical and isotope composition of the Amazon (and most likely of most rivers) bears a biological imprint.

Controls on oxygen response to climate change on the Northwest European Continental Shelf

&lt;p&gt;Dissolved oxygen in the ocean is an indicator of water quality and low concentrations can threaten ecosystem health. The main sources of marine oxygen are diffusion from the atmosphere and phytoplankton photosynthesis. Biological respiration and decomposition act to reduce oxygen concentrations. Under conditions of vertical stratification, the water column below the pycnocline is isolated from oxygen exchange with the atmosphere, photosynthesis may be limited by light availability and oxygen concentrations decrease. Climate change influences the oxygen cycle in two ways: 1) changing the hydrodynamic climate and 2) affecting rates of biogeochemical processes. The hydrodynamic climate affects the nutrient supply and so controls phytoplankton production while changes to water column stratification affects vertical mixing. Gas solubility decreases with increasing temperature so that oxygen uptake from the atmosphere is expected to decrease under increasing oceanic temperatures. Biological cycling rates increase with increasing temperature affecting photosynthesis, respiration and bacterial decomposition. It is not obvious whether changes in oxygen concentrations due to changing ecosystem processes will mitigate or reinforce the projected reduction from solubility changes.&lt;/p&gt;&lt;p&gt;The Northwest European Continental shelf (NWES) is a region of the northeast Atlantic that experiences seasonal stratification. We use the physics-biogeochemical model NEMO-ERSEM to study near-bed oxygen concentrations on the NWES under a high greenhouse gas emissions scenario (Representative Concentration Pathway (RCP) 8.5). We show that much of the NWES could experience low oxygen concentrations by 2100 and assess the relative impacts of changing temperature and ecosystem processes. Until about 2040 the impact of solubility dominates the oxygen change. The mean near-bed oxygen concentration is projected to decrease by 6.3% by 2100, of which 73% is due to solubility changes and the remainder to changes in the ecosystem. In the oxygen-depleted region in the eastern North Sea, 77% of the near-bed oxygen reduction is due to ecosystem processes.&lt;/p&gt;