A Parameterization of the Roughness Length for the Air-Sea Interface in Free Convection

The response of the upper ocean to the parameterization of the roughness length z ₀ on the air side of the air-sea interface is studied using a one-dimensional mixed-layer model. In particular, it is shown that in the free convection limit when both the wind speed and the friction velocity approach zero, the familiar Charnock formula for the momentum roughness, which relies solely on wind generation, can be modified to account for contributions arising from the thermally generated turbulence. Therefore, a new parameterization is proposed for the momentum roughness length which extends the Charnock formula down to zero friction velocity. The value of a parameter which enters in the new formulation is determined by making use of exsisting free convection surface flux parameterizations. The effect of the new parameterization on the model performance is tested using data from the ocean weathership station Papa (OWS P), and data from the Long-Term Upper-Ocean Study (LOTUS) experiment. Simulations were carried out using a recently developed one-dimensional, second-order, turbulence closure scheme over diurnal as well as seasonal time scales. The findings suggest that the new momentum roughness parameterization improves the overall agreement between the observed and simulated sea-surface temperature (SST).     

UV-visible spectroscopy of organic carbon particulate sampled from ethylene/air flames

A systematic comparison of spectra obtained with extra and in situ diagnostics in the soot preinception region of rich, premixed ethylene air flames suggests that combustion generated organic carbon (OC) particulate can be extracted from flames and isolated from other flame material for further chemical analysis. Both the trend with height above the burner and the form of UV fluorescence and absorption spectra from extra situ sampled material captured in water agree with those measured in situ. These results show that the OC particulate formed in flames is partially water soluble. However, the collection efficiency can be increased using less polar solvents, like acetonitrile and dichloromethane. The fluorescence spectra from the water samples are comprised both a naphthalene-like component and a broad band UV fluorescence component similar to that observed in situ which is attributed to flame generated OC particulate. The broad band UV fluorescence centered around 320 nm is also observed very early in flames and does not change considerably with increasing flame residence time. These results support previous hypotheses that the UV broad band fluorescence is from carbonaceous material comprised two-ring aromatics, formed earlier than soot in the flame, and is still present along with soot at higher heights or flame residence times.     

Report: Combustion Byproducts and Their Health Effects: Summary of the 10th International Congress

The 10th International Congress on Combustion Byproducts and their Health Effects was held in Ischia, Italy, from June 17-20, 2007. It is sponsored by the US NIEHS, NSF, Coalition for Responsible Waste Incineration (CRWI), and Electric Power Research Institute (EPRI). The congress focused on: the origin, characterization, and health impacts of combustion-generated fine and ultrafine particles; emissions of mercury and dioxins, and the development/application of novel analytical/diagnostic tools. The consensus of the discussion was that particle-associated organics, metals, and persistent free radicals (PFRs) produced by combustion sources are the likely source of the observed health impacts of airborne PM rather than simple physical irritation of the particles. Ultrafine particle-induced oxidative stress is a likely progenitor of the observed health impacts, but important biological and chemical details and possible catalytic cycles remain unresolved. Other key conclusions were: (1) In urban settings, 70% of airborne fine particles are a result of combustion emissions and 50% are due to primary emissions from combustion sources, (2) In addition to soot, combustion produces one, possibly two, classes of nanoparticles with mean diameters of?~10?nm and?~1?nm. (3) The most common metrics used to describe particle toxicity, viz. surface area, sulfate concentration, total carbon, and organic carbon, cannot fully explain observed health impacts, (4) Metals contained in combustion-generated ultrafine and fine particles mediate formation of toxic air pollutants such as PCDD/F and PFRs. (5) The combination of metal-containing nanoparticles, organic carbon compounds, and PFRs can lead to a cycle generating oxidative stress in exposed organisms.     

Analysis of exhausts emitted by i.c. engines and stationary burners, by means of u.v. extinction and fluorescence spectroscopy

Optical investigations of the exhausts emitted by internal combustion (i.c.) engines and a stationary burner were performed, in order to assess their relative role as sources of organic matter to the atmosphere. Extinction spectra of air-diluted exhausts in the 200-400 nm u.v. band reveal the expected existence of gaseous trace-species (NO, NO2 and SO2) and carbonaceous particulate matter (soot). In addition, after subtracting the absorption contribution from known species, a strong residual absorption band remains below 250 nm, which is attributed to organic aromatic matter, involving no more than two aromatic rings. A set of ex situ extinction and laser induced fluorescence (LIF) experiments were carried out on condensed combustion-water samples. Extinction measurements from the water samples show absorption spectra similar to those observed from air-diluted samples, which are attributed to low volatility organic compounds, as they are trapped in the condensed phase. Combining the indications of extinction data for both air-diluted and condensed samples, it is suggested that the absorbing species might be molecular clusters of one/two aromatic rings. LIF spectra from condensed samples evidence two fluorescence bands, centered above 300 and 400 nm, respectively, whose intensities correlate with the combustion regimes. Analogous optical analysis on rain samples, collected in an urban area, showed that rain absorption and fluorescence spectra are similar to those found in condensed exhaust samples, which is consistent with the prevailing contribution of i.c. engines to the urban air pollution. The combined experimental data suggest that the absorbing and fluorescent species trapped in the condensed samples are organic (aromatic) compounds, involving mostly one two aromatic rings structural units, since they do not absorb above 250 nm. The overall molecular weight of the trapped material is likely heavy as they show low volatility.     

Modeling aerosol formation in opposed-flow diffusion flames

The microstructures of atmospheric pressure, counter-flow, sooting, flat, laminar ethylene diffusion flames have been studied numerically by using a new kinetic model developed for hydrocarbon oxidation and pyrolysis. Modeling results are in reasonable agreement with experimental data in terms of concentration profiles of stable species and gas-phase aromatic compounds. Modeling results are used to analyze the controlling steps of aromatic formation and soot growth in counter-flow configurations. The formation of high molecular mass aromatics in diffusion controlled conditions is restricted to a narrow area close to the flame front where these species reach a molecular weight of about 1000 u. Depending on the flame configuration, soot formation is controlled by the coagulation of nanoparticles or by the addition of PAH to soot nuclei.     

Detection of combustion formed nanoparticles

UV–visible extinction and scattering and two extra situ sampling techniques: atomic force microscopy (AFM) and differential mobility analysis (DMA) are used to follow the evolution of the particles formed in flames. These particle sizing techniques were chosen because of their sensitivity to detect inception particles, which have diameters, d<5 nm, too small to be observed with typical particle measurement instrumentation. The size of the particles determined by AFM and DMA compares well with the size determined by in situ optical measurements, indicating that the interpretation of the UV–visible optical signal is quite good, and strongly showing the presence of d=2–4 nm particles. UV–visible extinction measurements are also used to determine the concentration of d=2–4 nm particles at the exhausts of practical combustion systems. A numerical model, able to reproduce the experimentally observed low coagulation rate of nanoparticles with respect to soot particles, is used to investigate the operating conditions in the combustion chamber and exhaust system for which 2–4 nm particles survive the exhaust or grow to larger sizes. Combustion generated nanoparticles are suspected to affect human and environmental health because of their affinity for water, small size, low rate of coagulation, and large surface area/weight ratio. The ability to isolate nanoparticles from soot particles in hydrosols collected from combustion may be useful for future analysis by a variety of techniques and toxicological assays.     

A modeling evaluation of the effect of chlorine on the formation of particulate matter in combustion

The effect of chlorine on the fuel-rich oxidation of hydrocarbons and on the molecular weight growth of aromatics is analyzed by simulating experiments featuring a model chlorinated additive CH3Cl in a jet-stirred/plug-flow reactor and premixed flames. The kinetic model used in this work emphasizes the role of resonantly stabilized radicals in the formation and growth of aromatics, and considers soot inception as the net effect of molecular weight growth and graphitization of aromatic structures. Chlorinated hydrocarbons decompose at temperatures significantly lower than hydrocarbons, producing reactive Cl-atoms, which have a strong tendency to go to HCl. The HCI, tying up the H-atoms, inhibits hydrocarbon oxidation. The model is able to predict not only the levels but the shape of the experiments quite well and also the surprising finding of an increased soot formation associated with lower PAH levels found in rich flames with significant levels of chlorine. Based on reaction kinetic analysis, chlorine addition to the fuel enhances soot formation by promoting the formation of aromatic-ring compounds and accelerating the abstraction of aromatic H-atoms from stable PAH molecules. This process activates the transformation of aromatics to soot.     

Structure of inorganic and carbonaceous particles emitted from heavy oil combustion

The combustion of heavy fuel oil for power generation is a great source of carbonaceous and inorganic particle emissions, even though the combustion technologies and their efficiency are improving. The information about the size distribution function of the particles originated by trace metals present into the fuels is not adequate. In this paper, we focused our attention on the larger distribution mode of both the carbonaceous and metallic particles. Isokinetic sampling was performed at the exhausts of two typical heavy oil flames and the samples were size-segregated by mean of an 8-stages Andersen impactor. Further investigation performed on the samples using electronic microscopy coupled with X-ray analysis (EDX) evidenced the presence of solid spherical particles, called plerosphere(1) as analogy with cenosphere, with typical dimensions ranging between 200 nm and 2-3 microm, whose atomic composition contains a large amount of the trace metals present in the parent oils (Fe, V, Ni, etc). EDX analyses revealed that the metal concentration increases as the plerosphere dimension decreases.