活性氮:多多益善?

尺度和范围 1790年,Jean Claude Chaptal将元素周期表中的第14个元素命名为"氮"[1].两个世纪后,氮在生物地球化学过程中的作用和其作为一种必需营养元素的重大功能得到了很好的理解.我们知道,人类(以及植物和动物)的生存离不开氮;大气中大量存在的氮气(N2)是植物和动物不能直接利用的一种化学形式;只有少数特殊的微生物能够将大气中的氮转化("固定")为植物、动物可以利用的活性氮(活性氮)[2];另一小群体的微生物能够将活性氮转化(反硝化)为氮气.     

The enigma of progress in denitrification research.

Humans have dramatically increased the amount of reactive nitrogen (primarily ammonium, nitrogen oxides, and organically bound N) circulating in the biosphere and atmosphere, creating a wide array of desirable products (e.g., food production) and undesirable consequences (e.g., eutrophication of aquatic ecosystems and air pollution). Only when this reactive N is converted back to the chemically unreactive dinitrogen (N2) form, do these cascading effects of elevated reactive N cease to be of concern. Among the quantitatively most important processes for converting reactive N to N2 gas is the biological process of classical denitrification, in which oxides of nitrogen are used as terminal electron acceptors in anaerobic respiration. This Invited Feature on denitrification includes a series of papers that integrate our current state of knowledge across terrestrial, freshwater, and marine systems on denitrification rates, controlling factors, and methodologies for measuring and modeling denitrification. In this paper, we present an overview of the role of denitrification within the broader N cycle, the environmental and health concerns that have resulted from human alteration of the N cycle, and a brief historical perspective on why denitrification has been so difficult to study. Despite over a century of research on denitrification and numerous recent technological advances, we still lack a comprehensive, quantitative understanding of denitrification rates and controlling factors across ecosystems. Inherent problems of measuring spatially and temporally heterogeneous N2 production under an N2-rich atmosphere account for much of this slow progress, but lack of interdisciplinary communication of research results and methodological developments has also impeded denitrification research. An integrated multidisciplinary approach to denitrification research, from upland terrestrial ecosystems, to small streams, river systems, estuaries, and continental shelf ecosystems, and to the open ocean, may yield new insights into denitrification across landscapes and waterscapes.     

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.     

Modeling sources of nutrients in rivers draining into the Bay of Bengal—a scenario analysis

Regional Environmental Change - We model future trends in river export of nutrients to the Bay of Bengal, and the sources of this pollution. We focus on total nitrogen (TN), total phosphorus (TP),...     

Secondary organic aerosol production from aqueous photooxidation of glycolaldehyde: Laboratory experiments

Organic particulate matter (PM) formed in the atmosphere (secondary organic aerosol; SOA) is a substantial yet poorly understood contributor to atmospheric PM. Aqueous photooxidation in clouds, fogs and aerosols is a newly recognized SOA formation pathway. This study investigates the potential for aqueous glycolaldehyde oxidation to produce low volatility products that contribute SOA mass. To our knowledge, this is the first confirmation that aqueous oxidation of glycolaldehyde via the hydroxyl radical forms glyoxal and glycolic acid, as previously assumed. Subsequent reactions form formic acid, glyoxylic acid, and oxalic acid as expected. Unexpected products include malonic acid, succinic acid, and higher molecular weight compounds, including oligomers. Due to (1) the large source strength of glycolaldehyde from precursors such as isoprene and ethene, (2) its water solubility, and (3) the aqueous formation of low volatility products (organic acids and oligomers), we predict that aqueous photooxidation of glycolaldehyde and other aldehydes in cloud, fog, and aerosol water is an important source of SOA and that incorporation of this SOA formation pathway in chemical transport models will help explain the current under-prediction of organic PM concentrations.     

Organosulfates from glycolaldehyde in aqueous aerosols and clouds: Laboratory studies

Secondary organic aerosol (SOA) formation is enhanced on acidic seed particles; SOA also forms during cloud processing reactions where acidic sulfate is prevalent. Recently several studies have focused on the identification of organosulfates in atmospheric aerosols or smog chamber experiments, and upon the mechanism of formation for these products. We identify several organosulfate products formed during the laboratory OH radical oxidation of dilute aqueous glycolaldehyde in the presence of sulfuric acid. We propose a radical–radical reaction mechanism as being consistent with formation of these products under our experimental conditions. Using a kinetics model we estimate that organosulfates account for less than 1% of organic matter formed from these precursors during cloud processing. However, in wet acidic aerosols, where precursors are highly concentrated and acidic sulfate makes up close to half of the aerosol mass, this radical–radical reaction could account for significant organosulfate production.     

SOA from methylglyoxal in clouds and wet aerosols: Measurement and prediction of key products

Aqueous OH radical oxidation of methylglyoxal in clouds and wet aerosols is a potentially important global and regional source of secondary organic aerosol (SOA). We quantify organic acid products of the aqueous reaction of methylglyoxal (30–3000 μM) and OH radical (approx. 4 × 10^?12 M), model their formation in the reaction vessel and investigate how the starting concentrations of precursors and the presence of acidic sulfate (0–840 μM) affect product formation. Predicted products were observed. The predicted temporal evolution of oxalic acid, pyruvic acid and total organic carbon matched observations at cloud relevant concentrations (30 μM), validating this methylglyoxal cloud chemistry, which is currently being implemented in some atmospheric models of SOA formation. The addition of sulfuric acid at cloud relevant concentrations had little effect on oxalic acid yields. At higher concentrations (3000 μM), predictions deviate from observations. Larger carboxylic acids (≥C₄) and other high molecular weight products become increasingly important as concentration increases, suggesting that small carboxylic acids are the major products in clouds while larger carboxylic acids and oligomers are important products in wet aerosols.     

Denitrification across landscapes and waterscapes: a synthesis.

Denitrification is a critical process regulating the removal of bioavailable nitrogen (N) from natural and human-altered systems. While it has been extensively studied in terrestrial, freshwater, and marine systems, there has been limited communication among denitrification scientists working in these individual systems. Here, we compare rates of denitrification and controlling factors across a range of ecosystem types. We suggest that terrestrial, freshwater, and marine systems in which denitrification occurs can be organized along a continuum ranging from (1) those in which nitrification and denitrification are tightly coupled in space and time to (2) those in which nitrate production and denitrification are relatively decoupled. In aquatic ecosystems, N inputs influence denitrification rates whereas hydrology and geomorphology influence the proportion of N inputs that are denitrified. Relationships between denitrification and water residence time and N load are remarkably similar across lakes, river reaches, estuaries, and continental shelves. Spatially distributed global models of denitrification suggest that continental shelf sediments account for the largest portion (44%) of total global denitrification, followed by terrestrial soils (22%) and oceanic oxygen minimum zones (OMZs; 14%). Freshwater systems (groundwater, lakes, rivers) account for about 20% and estuaries 1% of total global denitrification. Denitrification of land-based N sources is distributed somewhat differently. Within watersheds, the amount of land-based N denitrified is generally highest in terrestrial soils, with progressively smaller amounts denitrified in groundwater, rivers, lakes and reservoirs, and estuaries. A number of regional exceptions to this general trend of decreasing denitrification in a downstream direction exist, including significant denitrification in continental shelves of N from terrestrial sources. Though terrestrial soils and groundwater are responsible for much denitrification at the watershed scale, per-area denitrification rates in soils and groundwater (kg N x km(-2) x yr(-1)) are, on average, approximately one-tenth the per-area rates of denitrification in lakes, rivers, estuaries, continental shelves, or OMZs. A number of potential approaches to increase denitrification on the landscape, and thus decrease N export to sensitive coastal systems exist. However, these have not generally been widely tested for their effectiveness at scales required to significantly reduce N export at the whole watershed scale.     

Biodegradation of disodium cocoamphodiacetate by a wastewater microbial consortium.

Biodegradation of an amphoteric surfactant commonly used in personal care products, disodium cocoamphodiacetate (DSCADA), was evaluated. Results from respirometry experiments indicated that high levels of DSCADA (>216 mg/L) may be toxic to bacteria in wastewater treatment processes. Limited biodegradation, with 50% dissolved organic carbon (DOC) removal and 80% chemical oxygen demand removal was observed in batch assays, while complete removal of the parent compound, DSCADA, was noted. Oxygen biosensors were used to evaluate biodegradability of the metabolites present in the batch samples. Additional aerobic microbial activity was not detected in these samples, even with a residual DOC of approximately 45 mg/L. Results from this research indicate that biodegradability of DSCADA is limited and recalcitrant metabolites may be formed. Because DSCADA is a commonly used surfactant and is present in domestic and industrial wastewater, the associated risk posed by residual compounds should be carefully evaluated.