Planetary stewardship in an urbanizing world: beyond city limits.

Cities are rapidly increasing in importance as a major factor shaping the Earth system, and therefore, must take corresponding responsibility. With currently over half the world's population, cities are supported by resources originating from primarily rural regions often located around the world far distant from the urban loci of use. The sustainability of a city can no longer be considered in isolation from the sustainability of human and natural resources it uses from proximal or distant regions, or the combined resource use and impacts of cities globally. The world's multiple and complex environmental and social challenges require interconnected solutions and coordinated governance approaches to planetary stewardship. We suggest that a key component of planetary stewardship is a global system of cities that develop sustainable processes and policies in concert with its non-urban areas. The potential for cities to cooperate as a system and with rural connectivity could increase their capacity to effect change and foster stewardship at the planetary scale and also increase their resource security.

Effects of precursor concentration and acidic sulfate in aqueous glyoxal-OH radical oxidation and implications for secondary organic aerosol.

Previous experiments demonstrated that aqueous OH radical oxidation of glyoxal yields low-volatility compounds. When this chemistry takes place in clouds and fogs, followed by droplet evaporation (or if it occurs in aerosol water), the products are expected to remain partially in the particle phase, forming secondary organic aerosol (SOA). Acidic sulfate exists ubiquitously in atmospheric water and has been shown to enhance SOA formation through aerosol phase reactions. In this work, we investigate how starting concentrations of glyoxal (30-3000 microM) and the presence of acidic sulfate (0-840 microM) affect product formation in the aqueous reaction between glyoxal and OH radical. The oxalic acid yield decreased with increasing precursor concentrations, and the presence of sulfuric acid did not alter oxalic acid concentrations significantly. A dilute aqueous chemistry model successfully reproduced oxalic acid concentrations, when the experiment was performed at cloud-relevant concentrations (glyoxal <300 microM), but predictions deviated from measurements at increasing concentrations. Results elucidate similarities and differences in aqueous glyoxal chemistry in clouds and in wet aerosols. They validate for the first time the accuracy of model predictions at cloud-relevant concentrations. These results suggest that cloud processing of glyoxal could be an important source of SOA.

Composition of dissolved organic nitrogen in continental precipitation investigated by ultra-high resolution FT-ICR mass spectrometry.

The atmospheric transport of fixed nitrogen (N) is a critical component of the global N cycle that has been heavily impacted by human activities. It has been shown that organic N is an important contributor to atmospheric N, but its sources and composition are largely unknown. Rainwater samples collected in New Jersey were analyzed by negative and positive ion ultrahigh-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Elemental compositions of 402 N-containing compounds were determined and five main groups of compound classes were identified: compounds containing carbon, hydrogen, oxygen, and N detected as positive ions (CHON+), compounds containing CHON detected as negative ions (CHON-), compounds containing CHN detected as positive ions (CHN+), and CHON compounds that contain sulfur (S) detected as both positive and negative ions (CHONS+, CHONS-, respectively). The CHON+ compound class has the largest number of compounds detected (i.e., 281), with the majority, i.e., 207, containing only one N atom. The elemental ratios of these compounds and their detection in the positive ion mode suggest that they are compounds with reduced N functionality. Known contributors to secondary organic aerosol with anthropogenic sources were also identified including organonitrate compounds and nitrooxy organosulfates.

CMAQ model performance enhanced when in-cloud secondary organic aerosol is included: comparisons of organic carbon predictions with measurements.

Mounting evidence suggests that low-volatility (particle-phase) organic compounds form in the atmosphere through aqueous phase reactions in clouds and aerosols. Although some models have begun including secondary organic aerosol (SOA) formation through cloud processing, validation studies that compare predictions and measurements are needed. In this work, agreement between modeled organic carbon (OC) and aircraft measurements of water soluble OC improved for all 5 of the compared ICARTT NOAA-P3 flights during August when an in-cloud SOA (SOAcld) formation mechanism was added to CMAQ (a regional-scale atmospheric model). The improvement was most dramatic for the August 14th flight, a flight designed specifically to investigate clouds. During this flight the normalized mean bias for layer-averaged OC was reduced from -64 to -15% and correlation (r) improved from 0.5 to 0.6. Underpredictions of OC aloft by atmospheric models may be explained, in part, by this formation mechanism (SOAcld). OC formation aloft contributes to long-range pollution transport and has implications to radiative forcing, regional air quality and climate.

Transformation of the nitrogen cycle: recent trends, questions, and potential solutions.

Humans continue to transform the global nitrogen cycle at a record pace, reflecting an increased combustion of fossil fuels, growing demand for nitrogen in agriculture and industry, and pervasive inefficiencies in its use. Much anthropogenic nitrogen is lost to air, water, and land to cause a cascade of environmental and human health problems. Simultaneously, food production in some parts of the world is nitrogen-deficient, highlighting inequities in the distribution of nitrogen-containing fertilizers. Optimizing the need for a key human resource while minimizing its negative consequences requires an integrated interdisciplinary approach and the development of strategies to decrease nitrogen-containing waste.

Evidence for oligomer formation in clouds: reactions of isoprene oxidation products.

Electrospray ionization mass spectrometry (ESI-MS) was used to investigate product formation in laboratory experiments designed to study secondary organic aerosol (SOA) formation in clouds. It has been proposed that water soluble aldehydes derived from aromatics and alkenes, including isoprene, oxidize further in cloud droplets forming organic acids and, upon droplet evaporation, SOA. Pyruvic acid is an important aqueous-phase intermediate. Time series samples from photochemical batch aqueous phase reactions of pyruvic acid and hydrogen peroxide were analyzed for product formation. In addition to the monomers predicted by the reaction scheme, products consistent with an oligomer system were found when pyruvic acid and OH radical were both present. No evidence of oligomer formation was found in a standard mix composed of pyruvic, glyoxylic, and oxalic acids prepared in the same matrix as the samples analyzed using the same instrument conditions. The distribution of high molecular weight products is consistent with oligomers composed of the mono-, oxo-, and di-carboxylic acids expected from the proposed reaction scheme.

Dynamics and characterization of refractory dissolved organic matter produced by a pure bacterial culture in an experimental predator-prey system.

We studied the effects of a bacterium (Pseudomonas chlororaphis) and a bactivorous protozoan (Uronema sp.) on transformations of labile dissolved organic carbon (DOC). In 36-day time series experiments, bacteria were grown on glucose both with and without protozoa. We measured bulk organic carbon pools and used electrospray ionization mass spectrometry to characterize dissolved organic matter on a molecular level. Bacteria rapidly utilized glucose, depleting it to nondetectable levels and producing new DOC compounds of higher molecular weight within 2 days. Some of these new compounds, representing 3 to 5% of the initial glucose-C, were refractory and persisted for over a month. Other new compounds were produced and subsequently used by bacteria during the lag and exponential growth phases, pointing to a dynamic cycling of organic compounds. Grazers caused a temporary spike in the DOC concentration consisting of labile compounds subsequently utilized by the bacteria. Grazing did not increase the complexity of the DOC pool already established by the bacteria but did continually decrease the particulate organic carbon pool and expedited the conversion of glucose-C to CO2. After 36 days, 29% of initial glucose-C remained in pure bacteria cultures, while only 6% remained in cultures where a grazer was present. In this study the bacteria were the primary shapers of the complex DOC continuum, suggesting higher trophic levels possibly have less of an impact on the qualitative composition of DOC than previously assumed.

Atmospheric pressure mass spectrometry: a new analytical chemical characterization method for dissolved organic matter in rainwater.

The complex mixture of organic compounds in the atmosphere influences climate, air quality, and ecosystem processes. Atmospheric pressure electrospray ionization mass spectrometry (APESI-MS) was evaluated as a potential tool for direct measurement of the total suite of individual dissolved organic matter (DOM) compounds in rainwater. The APESI-MS response was linear to all DOM compounds of atmospheric significance examined as standard solutions. Urban precipitation samples from New Brunswick, NJ (USA) were analyzed by APESI-MS over the mass-to-charge (m/z) range 50-3,000. Over 95% of the m/z ions detected were in the low m/z range (50-500). Over 300 unique m/z ions were detected across the 11 rainwater samples indicating the complexity of the mixture of DOM in rainwater. Forty percent of the organic bases (positive mode detection) and 22% of the organic acids (negative mode) occurred in at least 6 of the 11 rainwater samples. Ions corresponding to the m/z of carboxylic acids standards (nonanedioic acid; 1,4-butanedicarboxylic acid; pentanedioic acid; hydroxybutanedioic acid; and butanedioic acid) and to reduced N standards (allylurea; caffeine; imidazole; and N-2-propenylurea) occurred in at least one of the 11 rainwater samples. Total dissolved organic carbon (DOC) estimated from the APESI-MS analysis and measured by standard DOC methods were not statistically different.