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.)

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

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

A Synthesis of Global Urbanization Projections

This chapter reviews recent literature on global projections of future urbanization, covering the population, economic and physical extent perspectives. We report on several recent findings based on studies and reports on global patterns of urbanization. Specifically, we review new literature that makes projections about the spatial pattern, rate, and magnitude of urbanization change in the next 30–50 years. While projections should be viewed and utilized with caution, the chapter synthesis reports on several major findings that will have significant socioeconomic and environmental impacts including the following: By 2030, world urban population is expected to increase from the current 3.4 billion to almost 5 billion; Urban areas dominate the global economy – urban economies currently generate more than 90 % of global Gross Value Added; From 2000 to 2030, the percent increase in global urban land cover will be over 200 % whereas the global urban population will only grow by a little over 70 %. Our synthesis of recent projections suggest that between 50%–60% of the total urban land in existence in 2030 will be built in the first three decades of the 21st century. Challenges and limitations of urban dynamic projections are discussed, as well as possible innovative applications and potential pathways towards sustainable urban futures

Resilience Management for Healthy Cities in a Changing Climate

Cities are experiencing multiple impacts from global environmental change, and the degree to which they will need to cope with and adapt to these challenges will continue to increase. We argue that a ‘complex systems and resilience management’ view may significantly help guide future urban development through innovative integration of, for example, grey, blue and green infrastructure embedded in flexible institutions (both formal and informal) for multi-functionality and improved health. For instance, the urban heat island effect will further increase city-centre temperatures during projected more frequent and intense heat waves. The elderly and people with chronic cardiovascular and respiratory diseases are particularly vulnerable to heat. Integrating vegetation and especially trees in the urban infrastructure helps reduce temperatures by shading and evapotranspiration. Great complexity and uncertainty of urban social-ecological systems are behind this heatwave-health nexus, and they need to be addressed in a more comprehensive manner. We argue that a systems perspective can lead to innovative designs of new urban infrastructure and the redesign of existing structures. Particularly to promoting the integration of grey, green and blue infrastructure in urban planning through institutional innovation and structural reorganization of knowledge-action systems may significantly enhance prospects for improved urban health and greater resilience under various scenarios of climate change.info:eu-repo/semantics/publishedVersio

Fine-Scale in Situ Measurement of Riverbed Nitrate Production and Consumption in an Armored Permeable Riverbed

Alteration of the global nitrogen cycle by man has increased nitrogen loading in waterways considerably, often with harmful consequences for aquatic ecosystems. Dynamic redox conditions within riverbeds support a variety of nitrogen transformations, some of which can attenuate this burden. In reality, however, assessing the importance of processes besides perhaps denitrification is difficult, due to a sparseness of data, especially in situ, where sediment structure and hydrologic pathways are intact. Here we show in situ within a permeable riverbed, through injections of 15N-labeled substrates, that nitrate can be either consumed through denitrification or produced through nitrification, at a previously unresolved fine (centimeter) scale. Nitrification and denitrification occupy different niches in the riverbed, with denitrification occurring across a broad chemical gradient while nitrification is restricted to more oxic sediments. The narrow niche width for nitrification is in effect a break point, with the switch from activity “on” to activity “off” regulated by interactions between subsurface chemistry and hydrology. Although maxima for denitrification and nitrification occur at opposing ends of a chemical gradient, high potentials for both nitrate production and consumption can overlap when groundwater upwelling is strong