Understanding nutrient loading and sources in the Bay of Bengal Large Marine Ecosystem

Inputs of nitrogen, phosphorous and dissolved silica from watersheds draining into the Bay of Bengal Large Marine Ecosystem are calculated for the present day and predictions made for 2030 and 2050 are presented. The major sources are identified and the Indicator of Coastal Eutrophication (ICEP) is calculated

Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry

Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50% of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Elemental compositions of 552 unique molecular species were determined in the mass range 50–500 Da in the rainwater. Four main groups of organic compounds were identified: compounds containing carbon, hydrogen, and oxygen (CHO) only, sulfur (S) containing CHOS compounds, nitrogen (N) containing CHON compounds, and S- and N- containing CHONS compounds. Organic acids commonly identified in precipitation were detected in the rainwater. Within the four main groups of compounds detected in the rainwater, oligomers, organosulfates, and nitrooxy-organosulfates were assigned based on elemental formula comparisons. The majority of the compounds identified are products of atmospheric reactions and are known contributors to secondary organic aerosol (SOA) formed from gas phase, aerosol phase, and in-cloud reactions in the atmosphere. It is suggested that the large uncharacterized component of SOA is the main contributor to the large uncharacterized component of rainwater organic matter

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA). Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM–10 mM) was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols

Relationship between river size and nutrient removal

Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 33 (2006): L06410, doi:10.1029/2006GL025845.We present a conceptual approach for evaluating the biological and hydrological controls of nutrient removal in different sized rivers within an entire river network. We emphasize a per unit area biological parameter, the nutrient uptake velocity (νf), which is mathematically independent of river size in benthic dominated systems. Standardization of biological parameters from previous river network models to νf reveals the nature of river size dependant biological activity in these models. We explore how geomorphic, hydraulic, and biological factors control the distribution of nutrient removal in an idealized river network, finding that larger rivers within a basin potentially exert considerable influence over nutrient exports.This work was funded by NASA-IDS (NNG04GH75G), NSF-LTER OCE-9726921, and NOAA (NA17RJ2612- 344 to Princeton U.)

Dynamics of N removal over annual time periods in a suburban river network

Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 113 (2008): G03038, doi:10.1029/2007JG000660.River systems are dynamic, highly connected water transfer networks that integrate a wide range of physical and biological processes. We used a river network nitrogen (N) removal model with daily temporal resolution to evaluate how elevated N inputs, saturation of the denitrification and total nitrate removal processes, and hydrologic conditions interact to determine the amount, timing and distribution of N removal in the fifth-order river network of a suburban 400 km2 basin. Denitrification parameters were based on results from whole reach 15NO3 tracer additions. The model predicted that between 15 and 33% of dissolved inorganic nitrogen (DIN) inputs were denitrified annually by the river system. Removal approached 100% during low flow periods, even with the relatively low and saturating uptake velocities typical of surface water denitrification. Annual removal percentages were moderate because most N inputs occurred during high flow periods when hydraulic conditions and temperatures are less favorable for removal by channel processes. Nevertheless, the percentage of annual removal occurring during above average flow periods was similar to that during low flow periods. Predicted river network removal proportions are most sensitive to loading rates, spatial heterogeneity of inputs, and the form of the removal process equation during typical base flow conditions. However, comparison with observations indicates that removal by the river network is higher than predicted by the model at moderately high flows, suggesting additional removal processes are important at these times. Further increases in N input to the network will lead to disproportionate increases in N exports due to the limits imposed by process saturation.This work was funded by NSF-DEB- 0614282, NSF-OCE-9726921, NSF-DEB-0111410, and NSF-BCS- 0709685

NLOAD : an interactive, web-based modeling tool for nitrogen management in estuaries

Author Posting. © Ecological Society of America, 2007. This article is posted here by permission of Ecological Society of America for personal use, not for redistribution. The definitive version was published in Ecological Applications 17, Supple. (2007): S17–S30, doi:10.1890/05-1460.1.Eutrophication of estuaries is an increasing global concern that requires development of new tools to identify causes, quantify conditions, and propose management options that address this environmental problem. Since eutrophication is often associated with increased inputs of land-derived nitrogen to estuaries, we developed NLOAD, a user-friendly, web-based tool that brings together six different published models that predict nitrogen loading to estuaries and two models that estimate nitrogen concentrations in coastal waters. Here we describe each of the models, demonstrate how NLOAD is designed to function, and then use the models in NLOAD to predict nitrogen loads to Barnegat Bay, New Jersey (USA). The four models that we used to estimate nitrogen loads to Barnegat Bay, when adjusted, all had similar results that matched well with measured values and indicated that Barnegat Bay receives roughly 26 kg N·ha−1·yr−1. Atmospheric deposition was the dominant source of nitrogen to Barnegat Bay, followed by fertilizer nitrogen. Wastewater in Barnegat Bay is diverted to an offshore outfall and contributes no nitrogen to the system. The NLOAD tool has an additional feature that allows managers to assess the effectiveness of a variety of management options to reduce nitrogen loads. We demonstrate this feature of NLOAD through simulations in which fertilizer inputs to the Barnegat Bay watershed are reduced. Even modest cutbacks in the use of fertilizers on agricultural fields and lawns can be shown to reduce the amount of N entering Barnegat Bay.Support for the NLOAD tool came from the Cooperative Institute for Coastal and Estuarine Environmental Technologies (CICEET, CICEET-UNH grants #02-610 and #04-833). Additional funding was received from Environmental Defense

Barnegat Bay-Little Egg Harbor Estuary : case study of a highly eutrophic coastal bay system

Author Posting. © The Author(s), 2007. This is the author's version of the work. It is posted here by permission of Ecological Society of America for personal use, not for redistribution. The definitive version was published in Ecological Applications 17 (2007): S3–S16, doi:10.1890/05-0800.1.The Barnegat Bay-Little Egg Harbor Estuary is classified here as a highly eutrophic estuary based on application of NOAA’s National Estuarine Eutrophication Assessment model. Because it is shallow, poorly flushed, and bordered by highly developed watershed areas, the estuary is particularly susceptible to the effects of nutrient loading. Most of this load (~50%) is from surface water inflow, but substantial fractions also originate from atmospheric deposition (~39%), and direct groundwater discharges (~11%). No point source inputs of nutrients exist in the Barnegat Bay watershed. Since 1980, all treated wastewater from the Ocean County Utilities Authority's regional wastewater treatment system has been discharged 1.6 km offshore in the Atlantic Ocean. Eutrophy causes problems in this system, including excessive micro- and macroalgal growth, harmful algal blooms (HABs), altered benthic invertebrate communities, impacted harvestable fisheries, and loss of essential habitat (i.e., seagrass and shellfish beds). Similar problems are evident in other shallow lagoonal estuaries of the Mid-Atlantic and South Atlantic regions. To effectively address nutrient enrichment problems in the Barnegat Bay-Little Egg Harbor Estuary, it is important to determine the nutrient loading levels that produce observable impacts in the system. It is also vital to continually monitor and assess priority indicators of water quality change and estuarine health. In addition, the application of a new generation of innovative models using web-based tools (e.g., NLOAD) will enable researchers and decision-makers to more successfully manage nutrient loads from the watershed. Finally, the implementation of stormwater retrofit projects should have beneficial effects on the system.Financial support of the Barnegat Bay National Estuary Program and Jacques Cousteau National Estuarine Research Reserve is gratefully acknowledged

Evolution from a first clinical demyelinating event to multiple sclerosis in the REFLEX trial: Regional susceptibility in the conversion to multiple sclerosis at disease onset and its amenability to subcutaneous interferon beta-1a

BACKGROUND AND PURPOSE: In the REFLEX trial (ClinicalTrials.gov identifier: NCT00404352), patients with a first clinical demyelinating event (FCDE) displayed significantly delayed onset of multiple sclerosis (MS; McDonald criteria) when treated with subcutaneous interferon β-1a (scIFNβ-1a) versus placebo. This post hoc analysis evaluated the effect of scIFNβ-1a on spatio-temporal evolution of disease activity, assessed by changes in T2 lesion distribution, in specific brain regions of such patients and its relationship with conversion to MS. METHODS: Post hoc analysis of baseline and 24-month MRI data from FCDE patients who received scIFNβ-1a 44 μg once or three times weekly, or placebo in the REFLEX trial. Patients were grouped according to McDonald MS status (converter/non-converter) or treatment (scIFNβ-1a/placebo). For each patient group, a baseline lesion probability map (LPM) and longitudinal new/enlarging and shrinking/disappearing LPMs were created. Lesion location/frequency of lesion occurrence were assessed in the white matter (WM). RESULTS: At Month 24, lesion frequency was significantly higher in the anterior thalamic radiation (ATR) and corticospinal tract (CST) of converters versus non-converters (p<0.05). Additionally, the overall distribution of new/enlarging lesions across the brain at Month 24 was similar in placebo- and scIFNβ-1a-treated patients (ratio: 0.95). Patients treated with scIFNβ-1a versus placebo showed significantly lower new lesion frequency in specific brain regions (cluster corrected): ATR (p=0.025), superior longitudinal fasciculus (p=0.042), CST (p=0.048), and inferior longitudinal fasciculus (p=0.048). CONCLUSIONS: T2 lesion distribution in specific brain locations predict conversion to McDonald MS and show significantly reduced new lesion occurrence after treatment with scIFNβ-1a in an FCDE population

A re-evaluation of the magnitude and impacts of anthropogenic atmospheric nitrogen inputs on the ocean

We report a new synthesis of best estimates of the inputs of fixed nitrogen to the world ocean via atmospheric deposition, and compare this to fluvial inputs and di-nitrogen fixation. We evaluate the scale of human perturbation of these fluxes. Fluvial inputs dominate inputs to the continental shelf, and we estimate about 75% of this fluvial nitrogen escapes from the shelf to the open ocean. Biological di-nitrogen fixation is the main external source of nitrogen to the open ocean, i.e. beyond the continental shelf. Atmospheric deposition is the primary mechanism by which land based nitrogen inputs, and hence human perturbations of the nitrogen cycle, reach the open ocean. We estimate that anthropogenic inputs are currently leading to an increase in overall ocean carbon sequestration of ~0.4% (equivalent to an uptake of 0.15 Pg C yr-1 and less than the Duce et al., 2008 estimate). The resulting reduction in climate change forcing from this ocean CO2 uptake is offset to a small extent by an increase in ocean N2O emissions. We identify four important feedbacks in the ocean atmosphere nitrogen system that need to be better quantified to improve our understanding of the perturbation of ocean biogeochemistry by atmospheric nitrogen inputs. These feedbacks are recycling of (1) ammonia and (2) organic nitrogen from the ocean to the atmosphere and back, (3) the suppression of nitrogen fixation by increased nitrogen concentrations in surface waters from atmospheric deposition, and (4) increased loss of nitrogen from the ocean by denitrification due to increased productivity stimulated by atmospheric inputs